Process for producing ruthenium complexes and intermediates thereof and their use in olefin metathesis

Abstract

The invention provides a new process for producing ruthenium complexes represented by the Formula 1. Invention provides also the use of ruthenium complexes represented by the Formula 1 as precatalysts and/or catalysts in olefin metathesis reactions.

Claims

1. A compound of a structure represented by the formula selected from 5c-5j: ##STR00080## ##STR00081## ##STR00082## ##STR00083##

2. A method for olefin metathesis reactions comprising treating an olefin with a compound represented by the Formulae 5c-5j according to claim 1 as a precatalyst or catalyst.

3. The method of claim 2 wherein the olefin metathesis reaction comprises ring-closing metathesis, homometathesis, cross-metathesis, ethenolysis, isomerization reactions, diastereoselective ring-rearrangement metathesis, “alkene-alkyne” (en-yn) metathesis, ring opening metathesis polymerization or metathetic depolymerization.

4. The method for olefin metathesis reactions of claim 2 comprising treating the olefin with the compound represented by the Formulae 5c-5j in the presence of a cyclic alkyl amino carbene ligand scavenger.

Description

(1) The present invention and its advantageous effects are shown in the figures, wherein:

(2) FIG. 1 shows structures of the compounds of the present invention;

(3) FIG. 2 shows graphs depicting relationship between area under the peak (AUP) on the chromatogram and the concentration (mg/mL) of the analysed compound for reaction of the Example XXXX;

(4) FIG. 3 shows graphs depicting relationship between area under the peak (AUP) on the chromatogram and the concentration (mg/mL) of the analysed compound for reaction of the Example XXXXI;

(5) FIG. 4 shows standard curve for product P9 of the Example XXXXVI.

(6) Terms used the present specification have the following meanings:

(7) The term “halogen atom” or “halogen” means an element selected from F, Cl, Br, I.

(8) The term “carbene” means a particle containing a neutral carbon atom of a valence number two and two unpaired (triplet state) or paired (singlet state) valence electrons. The term “carbene” encompasses also carbene analogues, wherein the carbon atom is replaced by other chemical element such as boron, silicon, germanium, tin, lead, nitrogen, phosphorus, sulphur, selenium, and tellurium.

(9) The term “alkyl” refers to a saturated, straight, or branched hydrocarbon substituent with an indicated carbon atom number. Examples of an alkyl substituent are -methyl, -ethyl, -n-propyl, -n-butyl, -n-pentyl, -n-hexyl, -n-heptyl, -n-octyl, -n-nonyl, and -n-decyl. Representative branched —(C1-C10)alkyls include -isopropyl, -sec-butyl, -isobutyl, -tert-butyl, -isopentyl, -neopentyl, -1-methylbutyl, -2-methylbutyl, -3-methylbutyl, -1,1-dimethylpropyl, -1,2-dimethylpropyl, -1-methylpentyl, -2-methylpentyl, -3-methylpentyl, -4-methylpentyl, -1-ethylbutyl, -2-ethylbutyl, -3-ethylbutyl, -1,1-dimethylbutyl, -1,2-dimethylbutyl, -1,3-dimethylbutyl, -2,2-dimethylbutyl, -2,3-dimethylbutyl, -3,3-dimethylbutyl, -1-methylhexyl, -2-methylhexyl, -3-methylhexyl, -4-methylhexyl, -5-methylhexyl, -1,2-dimethylpentyl, -1,3-dimethylpentyl, -1,2-dimethylhexyl, -1,3-dimethylhexyl, -3,3-dimethylhexyl, -1,2-dimethylheptyl, -1,3-dimethylheptyl, and -3,3-dimethylheptyl, and the like.

(10) The term “alkoxy” refers to an alkyl substituent as described above connected by an oxygen atom.

(11) The term “perfluoroalkyl” means an alkyl group as described above, in which all hydrogen atoms were replaced with the same or different type of halogen atoms.

(12) The term “cycloalkyl” refers to a saturated mono- or polycyclic hydrocarbon substituent with an indicated carbon atom number. Examples of a cycloalkyl substituent are -cyclopropyl, -cyclobutyl, -cyclopentyl, -cyclohexyl, -cycloheptyl, -cyclooctyl, -cyclononyl, -cyclodecyl, and the like.

(13) The term “alkenyl” refers to a saturated, straight, or branched acyclic hydrocarbon substituent with an indicated carbon atom number and containing at least one carbon-carbon double bond. Examples of an alkenyl substituent are -vinyl, -allyl, -1-butenyl, -2-butenyl, -isobutylenyl, -1-pentenyl, -2-pentenyl, -3-methyl-1-butenyl, -2-methyl-2-butenyl, -2,3-di-methyl-2-butenyl, -1-hexenyl, -2-hexenyl, -3-hexenyl, -1-heptenyl, -2-heptenyl, -3-heptenyl, -1-octenyl, -2-octenyl, -3-octenyl, -1-nonenyl, -2-nonenyl, -3-nonenyl, -1-decenyl, -2-decenyl, -3-decenyl, and the like.

(14) The term “cycloalkenyl” refers to a saturated mono- or polycyclic hydrocarbon substituent with an indicated carbon atom number and containing at least one carbon-carbon double bond. Examples of cycloalkenyl substituent are -cyclopentenyl, -cyclopentadienyl, -cyclohexenyl, -cyclohexadienyl, -cycloheptenyl, -cycloheptadienyl, -cycloheptatrienyl, -cyclooctenyl, -cyclooctadienyl, -cyclooctatrienyl, -cyclooctatetraenyl, -cyclononenyl, -cyclononadienyl, -cyclodecenyl, -cyclodecadienyl, and the like.

(15) The term “alkynyl” refers to a saturated, straight, or branched acyclic hydrocarbon substituent with an indicated carbon atom number and containing at least one carbon-carbon triple bond. Examples of an alkynyl substituent are -acetylenyl, -propynyl, -1-butynyl, -2-butynyl, -1-pentynyl, -2-pentynyl, -3-methylo-1-butynyl, -4-pentynyl, -1-hexynyl, -2-hexynyl, -5-hexynyl, and the like.

(16) The term “cycloalkynyl” refers to a saturated mono- or polycyclic hydrocarbon substituent with an indicated carbon atom number and containing at least one carbon-carbon triple bond. Examples of cycloalkynyl substituent are -cyclohexynyl, -cycloheptynyl, -cyclooctynyl, and the like.

(17) The term “aryl” refers to an aromatic mono- or polycyclic hydrocarbon substituent with an indicated carbon atom number. Examples of an aryl substituent are -phenyl, -tolyl, -xylyl, -naphthyl, -2,4,6-trimethylphenyl, -2-fluorophenyl, -4-fluorophenyl, -2,4,6-trifluorophenyl, -2,6-difluorophenyl, -4-nitrophenyl, and the like.

(18) The term “aralkyl” refers to an alkyl substituent, as described above, substituted with at least one aryl as described above. Examples of an aralkyl substituent are -benzyl, -diphenylmethyl, -triphenylmethyl, and the like.

(19) The term “heteroaryl” refers to an aromatic mono- or polycyclic hydrocarbon substituent with an indicated carbon atom number, wherein at least one carbon atom was replaced with a heteroatom selected from O, N and S atoms. Examples of heteroaryl substituent are -furyl, -thienyl, -imidazolyl, -oxazolyl, -thiazolyl, -isoxazolyl, triazolyl, -oxadiazolyl, -thiadiazolyl, -tetrazolyl, -pyridyl, -pyrimidyl, -triazinyl, -indolyl, -benzo[b]furyl, -benzo[b]thienyl, -indazolyl, -benzimidazolyl, -azaindolyl, -quinolyl, -isoquinolyl, -carbazolyl, and the like.

(20) The term “heterocycle” refers to a saturated or partly unsaturated, mono- or polycyclic hydrocarbon substituent with an indicated carbon atom number, wherein at least one carbon atom was replaced with a heteroatom selected from O, N and S atoms. Examples of a heterocyclic substituent are furyl, thiophenyl, pyrrolyl, oxazolyl, imidazolyl, thiazolyl, isoxazolyl, pyrazolyl, isothiazolyl, triazinyl, pyrrolidinonyl, pyrrolidinyl, hydantoinyl, oxiranyl, oxetanyl, tetrahydrofuranyl, tetrahydrothiophenyl, quinolinyl, isoquinolinyl, chromonyl, coumarinyl, indolyl, indolizinyl, benzo[b]furanyl, benzo[b]thiophenyl, indazolyl, purinyl, 4H-quinolizinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyridinyl, carbazolyl, β-carbolinyl, and the like.

(21) The term “neutral ligand” refers to an uncharged substituent, which is able to form a coordinate bond with a metal centre (ruthenium atom). Examples of such ligands may be: amines, phosphines and their oxides, alkyl and aryl phosphites and phosphates, arsines and their oxides, ethers, alkyl and aryl sulphides, coordinated hydrocarbons, alkyl and aryl halides.

(22) The term “indenylidene” refers to an unsaturated hydrocarbon substituent with an indene (benzocyclopentadiene) backbone linked via a double bond to a metal atom.

(23) The term “heteroindenylidene” refers to an indenylidene substituent, defined above, wherein at least one carbon atom was replaced with heteroatom from a group including nitrogen, oxygen, sulphur.

(24) The term “anionic ligand” refers to a substituent, which is able to form a coordinate bond with a metal centre (ruthenium atom) having a charge which is able to partially or totally compensate the charge of the metal centre. Examples of such ligands may be fluorine, chloride, bromide, iodide, cyanide, cyanate, and thiocyanate anions, carboxylic acid anions, alcohol anions, phenol anions, thiol and thiophenol anions, anions of hydrocarbons with a delocalised charge (e.g. cyclopentadiene), anions of (organo)sulphuric and (organo)phosphoric acids and esters thereof (such as e.g. anions of alkylsulphonic and arylsulphonic acids, anions of alkylphosphoric and arylophosphoric acids, anions of sulphuric acid alkyl and aryl esters, anions of phosphoric acid alkyl and aryl esters, anions of alkylphosphoric and arylphosphoric acid alkyl and aryl esters). Optionally, anionic ligand may have L.sup.1, L.sup.2 and L.sup.3 group, linked in the same way as catechol anion, acetylacetone anion, and salicylaldehyde anion. Anionic ligands (X.sup.1, X.sup.2) and neutral ligands (L.sup.1, L.sup.2, L.sup.3) can be combined together to form polydentate ligands, for example bidentate ligand (X.sup.1-X.sup.2), tridentate ligand (X.sup.1-X.sup.2-L.sup.1), tetradentate ligand (X.sup.1-X.sup.2-L.sup.1-L.sup.2), bidentate ligand (X.sup.1-L.sup.1), tridentate ligand (X.sup.1-L.sup.1-L.sup.2), tetradentate ligand (X.sup.1-L.sup.1-L.sup.2-L.sup.3), bidentate ligand (L.sup.1-L.sup.2), tridentate ligand (L.sup.1-L.sup.2-L.sup.3). Examples of such ligands are: catechol anion, acetylacetone anion, and salicylaldehyde anion.

(25) The term “heteroatom” means an atom selected from a group of oxygen, sulphur, nitrogen, phosphorus, and others.

(26) The term “chlorinated solvent” means a solvent containing in its structure at least one atom of fluorine, chlorine, bromine, or iodine; more preferably more than one. Examples of such solvents are dichloromethane, chloroform, tetrachloromethane (carbon tetrachloride), 1,2-dichloroethane, chlorobenzene, perfluorobenzene, perfluorotoluene, freons, and others.

(27) The term “nonpolar solvent” means a solvent characterised by a zero or very small dipole moment. Examples of such solvents are pentane, hexane, octane, nonane, decane, benzene, toluene, tetrahydrofuran (THF) and its derivatives, diethyl ether, dichloromethane, ethyl acetate, chloroform, and others.

(28) The term “DEDAM” means diethyl diallylmalonate, used as a model diene in RCM reactions comparing activities of available precatalysts and catalysts for olefin metathesis reactions.

(29) The term “GC” means gas chromatography.

(30) The term “HPLC” means high pressure liquid chromatography, and solvents designated as solvents for “HPLC” are solvents of suitable purity for HPLC analysis.

(31) The term “NMR” means nuclear magnetic resonance.

(32) The term “NHC” means N-heterocyclic carbene.

(33) The term “TLC” means thin layer chromatography.

(34) The term “alkenyne” means a compound having in its structure a double and triple bond (en-yne).

(35) The term “precatalyst” means, in the case of ruthenium complexes, a 16-electrone chemical compound, which after one ligand dissociation or molecular reorganisation step is converted into a proper 14-electrone olefin metathesis catalyst, which takes an active part in the catalytic cycle.

(36) Ruthenium complex compounds of the present invention are prepared by reactions shown on the following general reaction scheme, Scheme 1 and 2.

(37) ##STR00026## ##STR00027##

(38) Scheme 1 shows a general course of reactions in the individual steps of the method of preparation complex compounds represented by the Formula 1 according to the invention. First step is obtaining CAAC carbene in a deprotonation reaction of the CAAC salt using a suitable base. The most preferable bases are hexamethyldisilazane salts [metal bis(trimethylsilyl)amides] represented by the Formula MHMDS, wherein M is an alkali metal, such as potassium or lithium. Process of deprotonation or contacting together suitable reagents could conducted in many polar or nonpolar solvents. Preferably toluene is used as a solvent. In the following step, the CAAC carbene formed is contacted with first generation ruthenium complex containing in its structure two phosphine-type ligands.

(39) It has been shown, that the main product of this reaction is a second generation complex containing two CAAC ligands. In the TLC analysis one could observe also small amounts of the other second generation complex, which most probably contains one CAAC ligand and one phosphine ligand, Scheme 1 and 2.

(40) ##STR00028##

(41) The last process step is the addition of benzylidene ligand 4 to the mixture of unknown proportion of major and minor intermediates 5, in the presence of phosphine ligand scavenger and/or CAAC ligand scavenger (Scheme 2). Scheme 2 shows only the proposed course of 16-electrone ruthenium complex formation without detailed analysis of the metathesis process mechanism. Preferably, as a benzylidene ligand 2-isopropoxypropenylbenzene derivatives are used. It appeared that the preferable phosphine and/or CAAC ligand scavengers were copper(I) salts, including CuCl. Reactions shown in the Scheme 1 and 2 were conducted in a single reaction vessel without isolation of the intermediates (Embodiments I-XIV).

(42) To confirm that the intermediate compound 5 takes part actively in the preparation process of the precatalysts represented by the Formula 1, the previous one-pot type process was divided into two independent reaction parts, (a) and (b) in the Scheme 3. Ruthenium complexes represented by the general formula 5 were isolated and characterised with the NMR and MS analysis, confirming lack of phosphine ligand in the structure and presence of the two CAAC ligands. It has been shown, that compounds represented by the structure 5 in the reaction with benzylidene ligand 4 in the presence of CAAC ligand scavenger provide compounds represented by the Formula 1. Reactions for individual steps were shown in the Scheme 3 (part (a) in Embodiments XV, XVI and XVIII and part (b) in Embodiments XVII and XIX). Moreover, the inventors decided to check, whether intermediate compounds represented by the general formula 5 are active precatalysts in the olefin metathesis, what was shown in the Example XXII.

(43) ##STR00029##

(44) In the examples described below the preparation methods and use of the new ruthenium complexes of the invention were illustrated. The examples shown below are provided for the better understanding of the invention and they are not intended to limit its scope in any way. Examples of the catalyst preparation of the invention confirm higher process yields and more preferable ruthenium complex preparation parameters on the industrial scale. Comparative Examples with known complexes used confirm that complexes of the invention show different catalytic properties.

EMBODIMENTS OF THE INVENTION

Example I

(45) Preparation Method of Precatalyst 1a

(46) ##STR00030##

(47) To salt 3aa (1.73 g, 5.0 mmol, 2 molar equivalents) dry deoxygenated toluene (20 mL) was added in argon atmosphere. The mixture was heated to 80° C. and solution of LiHMDS in toluene (1 M, 5.0 mL, 5.0 mmol, 2 molar equivalents) was added. After 1 minute solid complex M10 (2.22 g, 2.5 mmol, 1 molar equivalent) was added. After 2 minutes the mixture was cooled down to 60° C. Benzylidene ligand 4a (0.529 g, 3.0 mmol, 1.2 molar equivalents) and CuCl (0.866 g, 8.75 mmol, 3.5 molar equivalents) were added. Reaction mixture was stirred for 5 minutes at 60° C. and cooled down to the room temperature. The crude product was isolated by column chromatography on silica gel (eluent: toluene). Green fraction was collected and concentrated to dryness. The residue was dissolved in ethyl acetate and filtrated. The solvent was evaporated, the residue was washed with isopropanol and dried under high vacuum giving green crystalline solid-precatalyst 1a (0.584 g, 40%).

(48) .sup.1H NMR (C.sub.6D.sub.6, 500 MHz): δ=16.41 (s, 1H), 7.33-7.28 (m, 1H), 7.22-7.18 (m, 2H), 7.16-7.11 (m, 1H), 7.01 (dd, J=7.6; 1.6 Hz, 1H), 6.64 (td, J=7.4; 0.8 Hz, 1H), 6.46-6.42 (m, 1H), 4.67 (septet, J=6.1 Hz, 1H), 2.87-2.78 (m, 2H), 2.45-2.35 (m, 2H), 2.23 (s, 6H), 1.77 (s, 2H), 1.70 (d, J=6.1 Hz, 6H), 0.97-0.92 (m, 12H) ppm.

Example II

(49) Preparation Method of Precatalyst 1a; Attempt with a Greater Amount of CAAC Salt 3aa—Here 3 Molar Equivalents.

(50) ##STR00031##

(51) To salt 3aa (1.40 g, 4.05 mmol, 3 molar equivalents) dry deoxygenated toluene (10 mL) was added in argon atmosphere. The mixture was heated to 80° C. and solution of LiHMDS in toluene (1 M, 4.05 mL, 4.05 mmol, 3 molar equivalents) was added. After 1 minute solid complex M10 (1.20 g, 1.35 mmol, 1 molar equivalent) was added. After 2 minutes the mixture was cooled down to 60° C. Ligand 4a (0.286 g, 1.62 mmol, 1.2 molar equivalents) and CuCl (0.601 g, 6.08 mmol, 4.5 molar equivalents) were added. Reaction mixture was stirred for 5 minutes at 60° C. and cooled down to the room temperature. The crude product was isolated by column chromatography on silica gel (eluent: toluene). Green fraction was collected and concentrated to dryness. The residue was dissolved in ethyl acetate and filtrated. The solvent was evaporated, the residue was washed with isopropanol and dried under high vacuum giving green crystalline solid-precatalyst 1a (0.408 g, 52%). Comparison with Example I.

Example III

(52) Preparation Method of Hoveyda-Type Precatalyst 1a Using Other First Generation Precursor, Here M1 (Umicore M1™)

(53) ##STR00032##

(54) To salt 3aa (1.06 g, 3.07 mmol, 2 molar equivalents) dry deoxygenated toluene (12 mL) was added in argon atmosphere. The mixture was heated to 80° C. and solution of LiHMDS in toluene (1 M, 3.07 mL, 3.07 mmol, 2 molar equivalents) was added. After 1 minute solid complex M1 (1.42 g, 1.53 mmol, 1 molar equivalent) was added. After 10 minutes the mixture was cooled down to 60° C. Benzylidene ligand 4a (0.325 g, 1.84 mmol, 1.2 molar equivalents) and CuCl (0.532 g, 5.37 mmol, 3.5 molar equivalents) were added. Reaction mixture was stirred for 10 minutes at 60° C. and cooled down to the room temperature. The crude product was isolated by column chromatography on silica gel (eluent: toluene). Green fraction was collected and concentrated to dryness. The residue was dissolved in ethyl acetate and filtrated. The solvent was evaporated, the residue was washed with isopropanol and dried under high vacuum giving green crystalline solid-precatalyst 1a (0.520 g, 58%). Comparison with the Example I.

Example IV

(55) Preparation Method of Precatalyst 1a Using Other First Generation Precursor, Here Gru-I.

(56) ##STR00033##

(57) To salt 3aa (1.04 g, 3.0 mmol, 2 molar equivalents) dry deoxygenated toluene (12 mL) was added in argon atmosphere. The mixture was heated to 80° C. and solution of LiHMDS in toluene (1 M, 3.0 mL, 3.0 mmol, 2 molar equivalents) was added. After 1 minute solid complex Gru-I (1.23 g, 1.5 mmol, 1 molar equivalent) was added. After 30 minutes the mixture was cooled down to 60° C. Benzylidene ligand 4a (0.317 g, 1.8 mmol, 1.2 molar equivalents) and CuCl (0.520 g, 5.25 mmol, 3.5 molar equivalents) were added. Reaction mixture was stirred for 10 minutes at 60° C. and cooled down to the room temperature. The crude product was isolated by column chromatography on silica gel (eluent: toluene). Green fraction was collected and concentrated to dryness. The residue was dissolved in ethyl acetate and filtrated. The solvent was evaporated, the residue was washed with isopropanol and dried under high vacuum giving green crystalline solid-precatalyst 1a (0.409 g, 47%). Comparison with Example I.

Example V

(58) Preparation Method of Precatalyst 1b Containing Nitro Group-Activated Benzylidene

(59) ##STR00034##

(60) To salt 3aa (3.45 g, 10.0 mmol, 2 molar equivalents) dry deoxygenated toluene (40 mL) was added in argon atmosphere. The mixture was heated to 80° C. and solution of LiHMDS in toluene (1 M, 10.0 mL, 10.0 mmol, 2 molar equivalents) was added. After 1 minute solid complex M10 (4.43 g, 5.0 mmol, 1 molar equivalent) was added. After 2 minutes the mixture was cooled down to 60° C. Benzylidene ligand 4b (1.33 g, 6.0 mmol, 1.2 molar equivalents) and CuCl (1.73 g, 17.5 mmol, 3.5 molar equivalents) were added. Reaction mixture was stirred for 5 minutes at 60° C. and cooled down to the room temperature. The crude product was isolated by column chromatography on silica gel (eluent: toluene). Green fraction was collected and concentrated to dryness. The residue was dissolved in ethyl acetate and filtrated. The solvent was evaporated, the residue was washed with isopropanol and dried under high vacuum giving green crystalline solid-precatalyst 1b (1.57 g, 50%).

(61) .sup.1H NMR (CD.sub.2Cl.sub.2, 500 MHz): δ=16.29 (s, 1H), 8.46 (dd, J=9.1; 2.7 Hz, 1H), 7.72-7.65 (m, 2H), 7.51 (d, J=7.7 Hz, 2H), 7.08 (d, J=8.7 Hz, 1H), 5.26 (septet, J=6.1 Hz, 1H), 2.61-2.49 (m, 4H), 2.21 (s, 2H), 2.07 (s, 6H), 1.77 (d, J=6.2 Hz, 6H), 1.33 (s, 6H), 0.91 (t, J=7.4 Hz, 6H) ppm.

(62) .sup.13C NMR (CD.sub.2Cl.sub.2, 125 MHz): δ=290.4, 263.8, 165.6, 157.1, 143.7, 143.4, 138.8, 129.9, 127.7, 125.7, 118.3, 113.7, 79.4, 78.2, 56.5, 52.3, 29.9, 28.9, 25.3, 22.4, 14.9 ppm.

(63) HRMS-ESI calculated for C.sub.28H.sub.39N.sub.2O.sub.3Ru [M-2Cl+H].sup.+: 553.2006; found: 553.2004.

(64) Elemental analysis: calculated for C.sub.28H.sub.38N.sub.2Cl.sub.2O.sub.3Ru:

(65) C, 54.02; H, 6.15; N, 4.50; Cl, 11.39; found: C, 54.18; H, 6.09; N, 4.42; Cl, 11.20.

Example VI

(66) Preparation Method of Precatalyst 1c Containing Hydroxamic Group-Activated Benzylidene

(67) ##STR00035##

(68) To salt 3aa (3.45 g, 10.0 mmol, 2 molar equivalents) dry deoxygenated toluene (40 mL) was added in argon atmosphere. The mixture was heated to 80° C. and solution of LiHMDS in toluene (1 M, 10.0 mL, 10.0 mmol, 2 molar equivalents) was added. After 1 minute solid complex M10 (4.43 g, 5.0 mmol, 1 molar equivalent) was added. After 2 minutes the mixture was cooled down to 60° C. Benzylidene ligand 4c (1.66 g, 6.0 mmol, 1.2 molar equivalents) and CuCl (1.73 g, 17.5 mmol, 3.5 molar equivalents) were added. Reaction mixture was stirred for 5 minutes at 60° C. and cooled down to the room temperature. The crude product was isolated by column chromatography on silica gel (eluent: toluene ->ethyl acetate/cyclohexane 3:7 v/v). Green fraction was collected and concentrated to dryness. The residue was dissolved in ethyl acetate and filtrated. The solvent was evaporated and the residue was dissolved in a minimal amount of methylene chloride and was added n-heptane. Methylene chloride was removed slowly on the evaporator, the resulting crystals were filtered off, washed with a small amount of n-heptane and dried under high vacuum giving green crystalline solid-precatalyst 1c (1.05 g, 31%).

(69) .sup.1H NMR (CD.sub.2Cl.sub.2, 500 MHz): δ=16.46 (s, 1H), 7.62-7.55 (m, 2H), 7.50-7.46 (m, 1H), 7.43-7.39 (m, 1H), 7.03 (d, J=8.3 Hz, 1H), 6.97 (t, J=7.4 Hz, 1H), 6.92-6.89 (m, 1H), 5.50 (d, J=7.5 Hz, 1H), 3.75 (s, 3H), 3.39 (s, 3H), 2.90 (dq, J=15.0; 7.4 Hz, 1H), 2.66 (dq, J=15.0; 7.4 Hz, 1H), 2.58 (dq, J=14.0; 7.0 Hz, 1H), 2.32 (q, J=7.5 Hz, 2H), 2.28 (s, 3H), 2.25-2.21 (m, 1H), 2.15-2.11 (m, 1H), 1.94 (s, 3H), 1.31 (s, 3H), 1.22 (s, 3H), 1.11 (t, J=7.4 Hz, 3H), 0.98 (dd, J=9.2; 6.9 Hz, 6H), 0.79 (t, J=7.4 Hz, 3H) ppm.

(70) .sup.13C NMR (CD.sub.2Cl.sub.2, 125 MHz): δ=305.2, 267.2, 170.0, 154.3, 146.0, 143.8, 143.4, 140.2, 130.0, 129.0, 127.2, 126.9, 123.6, 123.4, 113.2, 79.9, 79.8, 78.2, 62.3, 62.2, 56.3, 53.4, 32.6, 32.5, 31.3, 31.2, 30.9, 29.4, 29.3, 25.6, 25.5, 25.4, 25.1, 25.0, 19.9, 18.2, 14.8, 14.7, 14.6 ppm.

(71) HRMS-ESI calculated for C.sub.33H.sub.49N.sub.2O.sub.4Ru [M-2Cl+CH.sub.3O].sup.+: 639.2740; found: 639.2718.

(72) Elemental analysis: calculated for C.sub.32H.sub.46N.sub.2Cl.sub.2O.sub.3Ru:

(73) C, 56.63; H, 6.83; N, 4.13; Cl, 10.45; found: C, 56.63; H, 6.73; N, 4.01; Cl, 10.25.

Example VII

(74) Preparation Method of Precatalyst 1d

(75) ##STR00036##

(76) To salt 3ab (1.73 g, 5.0 mmol, 2 molar equivalents) dry deoxygenated toluene (20 mL) was added in argon atmosphere. The mixture was heated to 80° C. and solution of LiHMDS in toluene (1 M, 5.0 mL, 5.0 mmol, 2 molar equivalents) was added. After 1 minute solid complex M10 (2.22 g, 2.5 mmol, 1 molar equivalent) was added. After 2 minutes the mixture was cooled down to 60° C. Benzylidene ligand 4a (0.529 g, 3.0 mmol, 1.2 molar equivalents) and CuCl (0.866 g, 8.75 mmol, 3.5 molar equivalents) were added. Reaction mixture was stirred for 5 minutes at 60° C. and cooled down to the room temperature. The crude product was isolated by column chromatography on silica gel (eluent: toluene). Green fraction was collected and concentrated to dryness. The residue was dissolved in ethyl acetate and filtrated. The solvent was evaporated, the residue was washed with isopropanol and dried under high vacuum giving green crystalline solid-precatalyst 1d (0.688 g, 47%).

(77) .sup.1H NMR (CD.sub.2Cl.sub.2, 500 MHz): δ=16.20 (s, 1H), 7.60-7.53 (m, 2H), 7.50-7.47 (m, 1H), 7.29 (ddd, J=7.4; 1.7; 0.8 Hz, 1H), 6.97 (d, J=8.3 Hz, 1H), 6.92-6.85 (m, 2H), 5.16 (sept, J=6.1 Hz, 1H), 2.98 (sept, J=6.6 Hz, 1H), 2.24 (s, 3H), 2.23-2.16 (m, 2H), 2.13 (s, 3H), 2.02 (s, 3H), 1.75 (d, J=6.1 Hz, 3H), 1.71 (d, J=6.1 Hz, 3H), 1.40 (s, 3H), 1.36 (s, 3H), 1.28 (d, J=6.7 Hz, 3H), 0.67 (d, J=6.5 Hz, 3H) ppm.

Example VIII

(78) Preparation Method of Precatalyst 1d; Attempt with a Reduced Amount of CAAC Salt 3ab.

(79) ##STR00037##

(80) To salt 3ab (1.08 g, 3.13 mmol, 1.25 molar equivalents) dry deoxygenated toluene (22 mL) was added in argon atmosphere. The mixture was heated to 80° C. and solution of LiHMDS in toluene (1 M, 3.0 mL, 3.0 mmol, 1.2 molar equivalents) was added. After 1 minute solid complex M10 (2.22 g, 2.5 mmol, 1 molar equivalent) was added. After 2 minutes the mixture was cooled down to 60° C. Benzylidene ligand 4a (0.529 g, 3.0 mmol, 1.2 molar equivalents) and CuCl (0.619 g, 6.25 mmol, 2.5 molar equivalents) were added. Reaction mixture was stirred for 5 minutes at 60° C. and cooled down to the room temperature. The crude product was isolated by column chromatography on silica gel (eluent: toluene). Green fraction was collected and concentrated to dryness. The residue was dissolved in ethyl acetate and filtrated. The solvent was evaporated, the residue was washed with isopropanol and dried under high vacuum giving green crystalline solid-precatalyst 1d (0.596 g, 41%). Comparison with Example VI.

Example IX

(81) Preparation Method of Precatalyst 1e Containing Nitro Group-Activated Benzylidene

(82) ##STR00038##

(83) To salt 3ab (1.73 g, 5.0 mmol, 2 molar equivalents) dry deoxygenated toluene (20 mL) was added in argon atmosphere. The mixture was heated to 80° C. and solution of LiHMDS in toluene (1 M, 5.0 mL, 5.0 mmol, 2 molar equivalents) was added. After 1 minute solid complex M10 (2.22 g, 2.5 mmol, 1 molar equivalent) was added. After 2 minutes the mixture was cooled down to 60° C. Benzylidene ligand 4b (0.664 g, 3.0 mmol, 1.2 molar equivalents) and CuCl (0.866 g, 8.75 mmol, 3.5 molar equivalents) were added. Reaction mixture was stirred for 5 minutes at 60° C. and cooled down to the room temperature. The crude product was isolated by column chromatography on silica gel (eluent: toluene). Green fraction was collected and concentrated to dryness. The residue was dissolved in ethyl acetate and filtrated. The solvent was evaporated, the residue was washed with isopropanol and dried under high vacuum giving green crystalline solid-precatalyst 1e (0.663 g, 42%).

(84) .sup.1H NMR (CD.sub.2Cl.sub.2, 500 MHz): δ=16.19 (s, 1H), 8.45 (dd, J=9.1; 2.7 Hz, 1H), 7.70 (d, J=2.7 Hz, 1H), 7.65 (t, J=7.7 Hz, 1H), 7.55 (dd, J=8.0; 1.5 Hz, 1H), 7.35 (ddd, J=7.5; 1.6; 0.7 Hz, 1H), 7.08 (d, J=8.9 Hz, 1H), 5.26 (sept, J=6.2 Hz, 1H), 2.97 (sept, J=6.7 Hz, 1H), 2.26-2.19 (m, 5H), 2.13 (s, 3H), 2.03 (s, 3H), 1.77 (dd, J=16.1; 6.1 Hz, 6H), 1.43 (s, 3H), 1.38 (s, 3H), 1.30 (d, J=6.6 Hz, 3H), 0.68 (d, J=6.5 Hz, 3H) ppm.

(85) .sup.13C NMR (CD.sub.2Cl.sub.2, 125 MHz): δ=290.2, 264.6, 157.2, 149.1, 143.5, 143.4, 138.5, 138.4, 130.4, 130.0, 126.5, 125.8, 118.4, 113.7, 79.4, 78.2, 56.6, 52.3, 29.9, 29.7, 29.6, 29.1, 28.9, 26.3, 24.3, 22.4, 22.3, 21.8 ppm.

(86) HRMS-ESI calculated for C.sub.28H.sub.38ClN.sub.2O.sub.3Ru [M-Cl].sup.+: 587.1613; found: 587.1636.

(87) Elemental analysis: calculated for C.sub.28H.sub.38N.sub.2Cl.sub.2O.sub.3Ru:

(88) C, 54.02; H, 6.15; N, 4.50; Cl, 11.39; found: C, 54.19; H, 6.18; N, 4.37; Cl, 11.21.

Example X

(89) Preparation Method of Precatalyst 1f Containing Hydroxamic Group-Activated Benzylidene

(90) ##STR00039##

(91) To salt 3ab (1.73 g, 5.0 mmol, 2 molar equivalents) dry deoxygenated toluene (20 mL) was added in argon atmosphere. The mixture was heated to 80° C. and solution of LiHMDS in toluene (1 M, 5.0 mL, 5.0 mmol, 2 molar equivalents) was added. After 1 minute solid complex M10 (2.22 g, 2.5 mmol, 1 molar equivalent) was added. After 2 minutes the mixture was cooled down to 60° C. Benzylidene ligand 4c (0.832 g, 3.0 mmol, 1.2 molar equivalents) and CuCl (0.866 g, 8.75 mmol, 3.5 molar equivalents) were added. Reaction mixture was stirred for 5 minutes at 60° C. and cooled down to the room temperature. The crude product was isolated by column chromatography on silica gel (eluent: toluene ->ethyl acetate/cyclohexane 3:7 v/v). Green fraction was collected and concentrated to dryness. The residue was dissolved in ethyl acetate and filtrated. The solvent was evaporated and the residue was dissolved in a minimal amount of methylene chloride and n-heptane was added. Methylene chloride was removed slowly on the evaporator, the resulting crystals were filtered off, washed with a small amount of n-heptane and dried under high vacuum giving green crystalline solid-precatalyst 1f (0.390 g, 23%). A mixture of isomers A:B=1.8:1.

(92) Due to a very complex .sup.1H NMR spectrum only the characteristic benzylidene proton shifts were given: isomer A: singlet 16.42 ppm, isomer B: singlet 16.45 ppm (CD.sub.2Cl.sub.2).

(93) .sup.13C NMR (CD.sub.2Cl.sub.2, 125 MHz): δ=304.0 (A), 303.5 (B), 268.1 (B), 267.9 (A), 170.0 (A), 169.4 (B), 154.4 (A), 154.3 (B), 149.0 (B), 148.6 (A), 145.4 (B), 145.3 (A), 139.9 (B), 139.8 (A), 138.8 (A), 138.5 (B), 130.2 (A), 130.16 (B), 130.0 (A), 129.9 (B), 129.2 (B), 129.2 (A), 126.2 (B), 125.9 (A), 123.8 (B), 123.8 (A), 123.7 (B), 123.5 (A), 113.3 (B), 113.1 (A), 79.8 (B), 79.6 (A), 78.1 (B), 78.0 (A), 62.4 (A), 62.2 (B), 56.4 (B), 56.3 (A), 53.7 (A), 53.5 (B), 32.6 (A), 32.4 (B), 31.3 (A), 31.1 (B), 30.8 (B), 30.8 (B) 30.7 (A), 30.6 (A), 29.0 (B), 28.9 (A), 28.7 (B), 28.6 (A), 26.9, 24.9 (A), 24.8 (B), 22.3 (A), 21.7 (B), 20.0 (B), 19.9 (A), 18.2 ppm.

(94) HRMS-ESI calculated for C.sub.33H.sub.49N.sub.2O.sub.4Ru [M-2Cl+CH.sub.3O].sup.+: 639.2740; found: 639.2756.

(95) Elemental analysis: calculated for C.sub.32H.sub.46N.sub.2Cl.sub.2O.sub.3Ru:

(96) C, 56.63; H, 6.83; N, 4.13; Cl, 10.45; found: C, 56.69; H, 6.80; N, 4.07; Cl, 10.41.

Example XI

(97) Preparation Method of Precatalyst 1 g

(98) ##STR00040##

(99) To salt 3ac (0.413 g, 1.0 mmol, 2 molar equivalents) dry deoxygenated toluene (4 mL) was added in argon atmosphere. The mixture was heated to 80° C. and solution of LiHMDS in toluene (1 M, 1.0 mL, 1.0 mmol, 2 molar equivalents) was added. After 1 minute solid complex M10 (0.443 g, 0.5 mmol, 1 molar equivalent) was added. After 2 minutes the mixture was cooled down to 60° C. Benzylidene ligand 4a (0.106 g, 0.6 mmol, 1.2 molar equivalents) and CuCl (0.173 g, 1.75 mmol, 3.5 molar equivalents) were added. Reaction mixture was stirred for 25 minutes at 60° C. and cooled down to the room temperature. The crude product was isolated by column chromatography on silica gel (eluent: toluene). Green fraction was collected and concentrated to dryness. The residue was dissolved in ethyl acetate and filtrated. The solvent was evaporated, the residue was washed with isopropanol and dried under high vacuum giving green crystalline solid-precatalyst 1 g (0.118 g, 37%).

(100) .sup.1H NMR (C.sub.6D.sub.6, 500 MHz): δ=16.56 (s, 1H), 7.38-7.35 (m, 1H), 7.28-7.25 (m, 2H), 7.14-7.11 (m, 1H), 7.03-7.00 (m, 1H), 6.65 (t, J=7.4 Hz, 1H), 6.44 (d, J=8.3 Hz, 1H), 4.66 (sept, J=6.0 Hz, 1H), 3.77 (td, J=13.0; 3.4 Hz, 2H), 3.21 (sept, J=6.4 Hz, 2H), 2.50 (d, J=12.7 Hz, 2H), 1.93 (s, 2H), 1.90-1.85 (m, 2H), 1.74 (d, J=6.1 Hz, 6H), 1.70-1.60 (m, 2H), 1.43-1.34 (m, 2H), 1.16 (d, J=6.6 Hz, 6H), 1.00 (s, 6H), 0.93 (d, J=6.4 Hz, 6H) ppm.

Example XII

(101) Preparation Method of Precatalyst 1 g; Attempt with Other Base to Generate CAAC Carbene—Here KHMDS.

(102) ##STR00041##

(103) To salt 3ac (1.65 g, 4.0 mmol, 2 molar equivalents) dry deoxygenated toluene (12 mL) was added in argon atmosphere. The mixture was heated to 80° C. and solution of KHMDS in toluene (0.5M, 8.0 mL, 4.0 mmol, 2 molar equivalents) was added. After 1 minute solid complex M10 (1.77 g, 2.0 mmol, 1 molar equivalent) was added. After 2 minutes the mixture was cooled down to 60° C. Benzylidene ligand 4a (0.423 g, 2.4 mmol, 1.2 molar equivalents) and CuCl (0.693 g, 7.0 mmol, 3.5 molar equivalents) were added. Reaction mixture was stirred for 25 minutes at 60° C. and cooled down to the room temperature. The crude product was isolated by column chromatography on silica gel (eluent: toluene). Green fraction was collected and concentrated to dryness. The residue was dissolved in ethyl acetate and filtrated. The solvent was evaporated, the residue was washed with isopropanol and dried under high vacuum giving green crystalline solid-precatalyst 1 g (0.580 g, 45%). Comparison with Example XI.

Example XIII

(104) Preparation Method of Precatalyst 1h Containing Nitro Group-Activated Benzylidene

(105) ##STR00042##

(106) To salt 3ac (1.65 g, 4.0 mmol, 2 molar equivalents) dry deoxygenated toluene (16 mL) was added in argon atmosphere. The mixture was heated to 80° C. and solution of LiHMDS in toluene (1 M, 4.0 mL, 4.0 mmol, 2 molar equivalents) was added. After 1 minute solid complex M10 (1.77 g, 2.0 mmol, 1 molar equivalent) was added. After 2 minutes the mixture was cooled down to 60° C. Benzylidene ligand 4b (0.531 g, 2.4 mmol, 1.2 molar equivalents) and CuCl (0.693 g, 7.0 mmol, 3.5 molar equivalents) were added. Reaction mixture was stirred for 25 minutes at 60° C. and cooled down to the room temperature. The crude product was isolated by column chromatography on silica gel (eluent: toluene). Green fraction was collected and concentrated to dryness. The residue was dissolved in ethyl acetate and filtrated. The solvent was evaporated, the residue was washed with isopropanol and dried under high vacuum giving green crystalline solid-precatalyst 1h (0.550 g, 40%).

(107) .sup.1H NMR (CD.sub.2Cl.sub.2, 500 MHz): δ=16.42 (s, 1H), 8.44 (dd, J=9.1; 2.7 Hz, 1H), 7.71 (t, J=7.8 Hz, 1H), 7.65 (d, J=2.7 Hz, 1H), 7.51 (d, J=7.8 Hz, 2H), 7.10-7.07 (m, 1H), 5.25 (sept, J=5.9 Hz, 1H), 3.30-3.21 (m, 2H), 2.96 (sept, J=6.6 Hz, 2H), 2.31 (s, 2H), 2.28-2.22 (m, 2H), 1.96-1.89 (m, 2H), 1.78 (d, J=6.1 Hz, 6H), 1.60-1.46 (m, 4H), 1.35 (s, 6H), 1.26 (d, J=6.6 Hz, 6H), 0.64 (d, J=6.4 Hz, 6H) ppm.

(108) .sup.13C NMR (CD.sub.2Cl.sub.2, 125 MHz): δ=288.9, 264.7, 157.5, 148.7, 143.3, 142.9, 136.7, 130.4, 126.5, 125.7, 118.4, 113.8, 79.0, 78.2, 62.8, 44.9, 35.3, 30.8, 28.9, 26.8, 26.1, 24.6, 23.6, 22.5 ppm.

(109) HRMS-ESI calculated for C.sub.33H.sub.47N.sub.2O.sub.3Ru [M-2Cl+H].sup.+: 621.2634; found: 621.2630.

(110) Elemental analysis: calculated for C.sub.33H.sub.46N.sub.2Cl.sub.2O.sub.3Ru:

(111) C, 57.38; H, 6.71; N, 4.06; Cl, 10.27; found: C, 57.27; H, 6.58; N, 4.18; Cl, 10.12.

Example XIV

(112) Preparation Method of Precatalyst 1i Containing Hydroxamic Group-Activated Benzylidene

(113) ##STR00043##

(114) To salt 3ac (1.16 g, 2.8 mmol, 2 molar equivalents) dry deoxygenated toluene (11 mL) was added in argon atmosphere. The mixture was heated to 80° C. and solution of LiHMDS in toluene (1 M, 2.8 mL, 2.8 mmol, 2 molar equivalents) was added. After 1 minute solid complex M10 (1.24 g, 1.4 mmol, 1 molar equivalent) was added. After 2 minutes the mixture was cooled down to 60° C. Benzylidene ligand 4c (0.466 g, 1.68 mmol, 1.2 molar equivalents) and CuCl (0.485 g, 4.9 mmol, 3.5 molar equivalents) were added. Reaction mixture was stirred for 5 minutes at 60° C. and cooled down to the room temperature. The crude product was isolated by column chromatography on silica gel (eluent: toluene ->ethyl acetate/cyclohexane 3:7 v/v). Green fraction was collected and concentrated to dryness. The residue was dissolved in ethyl acetate and filtrated. The solvent was evaporated and the residue was dissolved in a minimal amount of methylene chloride and n-heptane was added. Methylene chloride was removed slowly on the evaporator, the resulting crystals were filtered off, washed with a small amount of n-heptane and dried under high vacuum giving green crystalline solid-precatalyst 1i (0.324 g, 31%).

(115) .sup.1H NMR (CD.sub.2Cl.sub.2, 500 MHz): δ=16.74 (s, 1H), 7.62-7.55 (m, 1H), 7.48-7.38 (m, 2H), 7.28 (d, J=7.7 Hz, 1H), 7.07 (d, J=8.4 Hz, 1H), 6.93 (td, J=7.4; 0.8 Hz, 1H), 6.84 (dd, J=7.5; 1.7 Hz, 1H), 5.51 (d, J=8.3 Hz, 1H), 3.73 (s, 3H), 3.35 (s, 3H), 3.16 (sept, J=6.5 Hz, 1H), 2.80-2.70 (m, 2H), 2.65 (sept, J=6.7 Hz, 1H), 2.22 (t, J=6.3 Hz, 2H), 1.36 (s, 3H), 1.33 (s, 3H), 1.32-1.28 (m, 6H), 1.25 (s, 3H), 1.19 (dd, J=15.4; 6.6 Hz, 6H), 0.98 (dd, J=8.8; 6.8 Hz, 6H), 0.76 (d, J=6.3 Hz, 3H), 0.57 (d, J=6.4 Hz, 3H) ppm.

(116) .sup.13C NMR (CD.sub.2Cl.sub.2, 125 MHz): δ=299.3, 267.8, 169.1, 154.6, 148.8, 148.6, 145.1, 144.1, 137.8, 132.9, 130.2, 130.0, 129.7, 126.3, 126.0, 125.1, 124.2, 123.4, 113.4, 81.5, 79.5, 78.1, 62.3, 62.1, 58.3, 45.8, 45.5, 37.3, 35.5, 34.6, 32.5, 32.0, 31.7, 30.2, 29.9, 29.6, 29.1, 28.6, 27.5, 27.2, 26.5, 25.8, 25.6, 25.0, 24.8, 24.0, 23.8, 23.7, 22.4, 19.9, 18.3 ppm.

(117) LRMS-ESI calculated for C.sub.38H.sub.57N.sub.2O.sub.4Ru [M-2Cl+CH.sub.3O].sup.+: 707.3; found: 707.3.

(118) HRMS-ESI calculated for C.sub.37H.sub.54N.sub.2O.sub.3NaCl.sub.2Ru [M+Na].sup.+: 769.2453; found 769.2437.

Example XV

(119) Preparation Method of Intermediate 5a from First Generation Precursor M1.

(120) ##STR00044##

(121) To salt 3aa (1.20 g, 3.48 mmol, 2 molar equivalents) dry deoxygenated toluene (14 mL) was added in argon atmosphere. The mixture was heated to 80° C. and solution of LiHMDS in toluene (1 M, 3.48 mL, 3.48 mmol, 2 molar equivalents) was added. After 1 minute solid complex M1 (1.60 g, 1.74 mmol, 1 molar equivalent) was added. After 20 minutes the mixture was cooled down to the room temperature. Reaction mixture was filtrated through a small amount of silica gel and washed with toluene. The crude product was isolated by column chromatography on silica gel (eluent: ethyl acetate/cyclohexane 1:9 v/v). Red fraction was collected and concentrated to dryness. It was dissolved in n-pentane and slowly concentrated to dryness (the product crystallised during solvent removal). Red crystalline solid was obtained—an intermediate compound 5a (1.07 g, 70%).

(122) .sup.1H NMR (C.sub.6D.sub.6, 500 MHz): δ=9.74 (d, J=7.7 Hz, 0.25H), 9.09 (d, J=7.3 Hz, 0.5H), 8.16 (s, 0.25H), 7.95-7.75 (m, 2H), 7.55-7.18 (m, 6H), 7.10-6.20 (m, 7H), 3.86-3.66 (m, 1H), 3.30-2.50 (m, 6H), 2.37 (d, J=13.0 Hz, 9H), 1.75-1.22 (m, 12H), 1.10-0.85 (m, 20H) ppm.

(123) .sup.13C NMR (CD.sub.2Cl.sub.2, 125 MHz): δ=279.9, 278.5, 277.8, 276.2, 145.5, 144.1, 143.6, 143.5, 141.3, 141.1, 140.8, 140.7, 140.2, 139.0, 138.6, 138.4, 137.9, 137.6, 134.3, 134.1, 130.6, 129.8, 129.4, 129.2, 128.2, 127.9, 127.6, 127.4, 127.0, 126.9, 126.7, 125.7, 125.5, 124.9, 124.7, 116.5, 116.1, 81.3, 79.7, 61.5, 56.9, 56.4, 55.0, 34.7, 32.5, 32.0, 31.5, 31.0, 30.5, 30.3, 30.0, 29.9, 29.6, 29.2, 27.5, 27.4, 25.3, 25.2, 24.7, 22.9, 14.8, 14.7, 14.4, 13.5, 13.2, 12.9 ppm.

(124) LRMS-ESI calculated for C.sub.51H.sub.64ClN.sub.2Ru [M-Cl].sup.+: 841.4; found: 841.4.

(125) HRMS-ESI calculated for C.sub.51H.sub.64N.sub.2Cl.sub.2Ru [M.].sup.+: 876.3490; found 876.3471.

(126) Elemental analysis: calculated for C.sub.51H.sub.64N.sub.2Cl.sub.2Ru:

(127) C, 69.84; H, 7.36; N, 3.19; Cl, 8.08; found: C, 69.88; H, 7.22; N, 3.21; Cl, 8.05.

Example XVI

(128) Preparation Method of Intermediate 5a from Precursor M1—Attempt with a Greater Amount CAAC Salt 3aa—Here 3 Molar Equivalents.

(129) ##STR00045##

(130) To salt 3aa (1.40 g, 4.05 mmol, 3 molar equivalents) dry deoxygenated toluene (10 mL) was added in argon atmosphere. The mixture was heated to 80° C. and solution of LiHMDS in toluene (1 M, 4.05 mL, 4.05 mmol, 3 molar equivalents) was added. After 1 minute solid complex M1 (1.25 g, 1.35 mmol, 1 molar equivalent) was added. After 5 minutes the mixture was cooled down to the room temperature. Reaction mixture was filtrated through a small amount of silica gel and washed with toluene. The crude product was isolated by column chromatography on silica gel (eluent: ethyl acetate/cyclohexane 1:9 v/v). Red fraction was collected and concentrated to dryness. It was dissolved in n-pentane and slowly concentrated to dryness (the product crystallised during solvent removal). Red crystalline solid was obtained—an intermediate compound 5a (1.02 g, 86%). Comparison with Example XV.

Example XVII

(131) Preparation Method of Precatalyst 1a—One-Step Procedure from Intermediate 5a.

(132) ##STR00046##

(133) To the solution of an intermediate 5a (0.948 g, 1.08 mmol, 1 molar equivalent) in dry deoxygenated toluene (10 mL) at 60° C. benzylidene ligand 4a (0.228 g, 1.29 mmol, 1.2 molar equivalents) and CuCl (0.214 g, 2.16 mmol, 2 molar equivalents) were added. Reaction mixture was stirred for 30 minutes and cooled down to the room temperature. The crude product was isolated by column chromatography on silica gel (eluent: toluene). Green fraction was collected and concentrated to dryness. The residue was dissolved in ethyl acetate and filtrated. The solvent was evaporated, the residue was washed with isopropanol and dried under high vacuum giving green crystalline solid-precatalyst 1a (0.390 g, 62%).

Example XVIII

(134) Preparation Method of Intermediate 5b from First Generation Precursor Gru-I.

(135) ##STR00047##

(136) To salt 3aa (2.76 g, 8.0 mmol, 2 molar equivalents) dry deoxygenated toluene (32 mL) was added in argon atmosphere. The mixture was heated to 80° C. and solution of LiHMDS in toluene (1 M, 8.0 mL, 8.0 mmol, 2 molar equivalents) was added. After 2 minutes solid complex Gru-I (3.29 g, 4.0 mmol, 1 molar equivalent) was added. After 25 minutes the mixture was cooled down to the room temperature. Reaction mixture was filtrated through a small amount of silica gel and washed with toluene. The crude product was isolated by column chromatography on silica gel (eluent: ethyl acetate/cyclohexane 1:9 v/v). Brown fraction was collected and concentrated to dryness. It was dissolved in n-pentane and slowly concentrated (the product crystallised during solvent removal). It was filtrated off and washed with cold n-pentane. Brown crystalline solid was obtained—an intermediate compound 5b (1.55 g, 50%).

(137) A mixture of isomers A:B=3.2:1. Due to a very complex .sup.1H NMR spectrum only the characteristic benzylidene proton shifts were given: isomer A: singlet 17.60 ppm, isomer B: singlet 18.52 ppm (CD.sub.2Cl.sub.2).

(138) .sup.13C NMR (CD.sub.2Cl.sub.2, 125 MHz): δ=283.7, 280.0, 279.9, 278.7, 150.6, 148.3, 143.7, 143.1, 141.6, 141.0, 140.7, 139.7, 139.0, 138.3, 132.5, 131.7, 131.3, 129.7, 128.5, 128.4, 127.7, 127.5, 127.4, 127.3, 127.2, 125.7, 125.5, 125.1, 124.8, 81.0, 79.5, 79.4, 59.0, 56.7, 56.1, 53.7, 53.4, 32.3, 31.7, 31.1, 30.9, 30.6, 30.2, 29.6, 29.0, 28.5, 28.2, 27.3, 27.1, 25.7, 25.4, 24.4, 22.9, 15.2, 14.9, 14.5, 14.4, 12.5, 12.4 ppm.

(139) LRMS-ESI calculated for C.sub.43H.sub.60ClN.sub.2Ru [M-Cl].sup.+: 741.3; found: 741.3.

(140) HRMS-ESI calculated for C.sub.43H.sub.60N.sub.2Cl.sub.2Ru [M.].sup.+: 776.3177; found 776.3156.

(141) Elemental analysis: calculated for C.sub.43H.sub.60N.sub.2Cl.sub.2Ru:

(142) C, 66.47; H, 7.78; N, 3.61; Cl, 9.13; found: C, 66.42; H, 7.75; N, 3.59; Cl, 9.18.

Example XIX

(143) Preparation Method of Precatalyst 1a from Intermediate 5b.

(144) ##STR00048##

(145) To the solution of intermediate 5b (0.801 g, 1.03 mmol, 1 molar equivalent) in dry deoxygenated toluene (10 mL) at 60° C. benzylidene ligand 4a (0.217 g, 1.23 mmol, 1.2 molar equivalents) and CuCl (0.204 g, 2.06 mmol, 2 molar equivalents) were added. Reaction mixture was stirred for 10 minutes and cooled down to the room temperature. The crude product was isolated by column chromatography on silica gel (eluent: toluene). Green fraction was collected and concentrated to dryness. The residue was dissolved in ethyl acetate and filtrated. The solvent was evaporated, the residue was washed with isopropanol and dried under high vacuum giving green crystalline solid-precatalyst 1a (0.385 g, 65%).

Example XX

(146) Preparation Method of Precatalyst 1j Containing Hydroxamic Group-Activated Benzylidene and Iodide Ligands.

(147) ##STR00049##

(148) To suspension of sodium iodide (1.04 g, 6.97 mmol, 30 molar equivalents) in acetone (2.3 mL) solid-precatalyst 1c (0.158 g, 0.232 mmol, 1 molar equivalent) was added. The whole was stirred at room temperature for 3 hours and then concentrated to dryness. The residue was dissolved in methylene chloride and inorganic salts were removed by filtration. The residue was filtrated through a small amount of silica gel (eluent ethyl acetate/cyclohexane 3:7 v/v). The solvent was evaporated and the residue was dissolved in a minimal amount of methylene chloride and n-heptane was added. Methylene chloride was removed slowly on the evaporator, the resulting crystals were filtered off, washed with a small amount of n-heptane and dried under high vacuum giving green crystalline solid 1j (0.178 g, 89%).

(149) .sup.1H NMR (CD.sub.2Cl.sub.2, 500 MHz): δ=15.83 (s, 1H), 7.60 (dt, J=8.7; 4.6 Hz, 1H), 7.57-7.52 (m, 1H), 7.47-7.44 (m, 1H), 7.42-7.38 (m, 1H), 7.03 (d, J=8.3 Hz, 1H), 6.95 (d, J=4.5 Hz, 2H), 5.50 (d, J=7.7 Hz, 1H), 3.87 (s, 3H), 3.41 (s, 3H), 3.24 (dq, J=15.1; 7.5 Hz, 1H), 2.80-2.62 (m, 3H), 2.44-2.36 (m, 4H), 2.24-2.20 (m, 1H), 2.15 (s, 3H), 2.14-2.10 (m, 1H), 1.35 (s, 3H), 1.26 (s, 3H), 1.20 (t, J=7.4 Hz, 3H), 1.04 (dd, J=7.0; 5.3 Hz, 6H), 0.94 (t, J=7.4 Hz, 3H) ppm.

(150) .sup.13C NMR (CD.sub.2Cl.sub.2, 125 MHz): δ=306.5, 271.3, 170.8, 155.0, 146.3, 144.1, 143.7, 140.3, 130.2, 129.0, 127.3, 127.0, 123.8, 123.3, 113.6, 80.9, 78.4, 62.5, 55.7, 53.2, 35.2, 34.8, 33.4, 32.6, 30.0, 29.5, 27.2, 26.7, 20.8, 18.6, 15.5, 15.3 ppm.

(151) HRMS-ESI calculated for C.sub.32H.sub.46IN.sub.2O.sub.3Ru [M-I].sup.+: 735.1600; found: 735.1636.

(152) Elemental analysis: calculated for C.sub.32H.sub.46N.sub.2I.sub.2O.sub.3Ru:

(153) C, 44.61; H, 5.38; N, 3.25; I, 29.46; found: C, 44.47; H, 5.37; N, 3.21; I, 29.29.

Example XXI

(154) Application of Precatalysts 1a-1j in Ring-Closing Metathesis (RCM) Reactions of Diethyl Diallylomalonate S1 Leading to a Cyclic Compound P1.

(155) ##STR00050##

(156) To the solution of diethyl diallylomalonate S1 (120.1 mg, 0.5 mmol) in dry deoxygenated toluene (5 mL) at 29° C. a solution of respective precatalyst (1a-1j), 0.1 mol %) in dry deoxygenated toluene (50 μL) was added. It was stirred in argon atmosphere. At certain time intervals 0.1 mL samples of reaction mixture were collected to which one drop of ethyl vinyl ether was added to deactivate the catalyst. The substrate conversion as a function of time was determined by GC analysis. A summary is presented in Table 1.

(157) TABLE-US-00001 TABLE 1 DEDAM conversion as a function of time. Time Conversion (%) (min) 1a 1b 1c 1d 1e 1f 1g 1h 1i 1j 5 6 10 67 6 9 80 — — — 5 10 19 32 87 16 31 94 — — — 20 20 43 63 95 38.5 71 98 — — — 47 30 62 76 97 54 86 99 — — — 60 45 77 85 98 68 93 99.5 — — — 71 60 84 90 98.5 77 95 99.5 — — — 77 120 92 95 99 88 98 99.5 — — — 86 180 — — — 91 99 99.6 2.3 5 30 89

Example XXII

(158) Application of Precatalyst 5a in Ring-Closing Metathesis (RCM) Reactions of Diethyl Diallylomalonate S1 Leading to Cyclic Compound P1.

(159) ##STR00051##

(160) To the solution of diethyl diallylomalonate S1 (480.6 mg, 2.0 mmol) in dry deoxygenated toluene (20 mL) at 60° C. a solution of precatalyst 5a (1.75 mg, 0.002 mmol, 0.1 mol %) in dry deoxygenated toluene (50 μL) was added. In case of reaction with CAAC carbene scavenger, CuCl (1.98 mg, 0.02 mmol) was added to the reaction mixture. The whole was stirred in argon atmosphere. At certain time intervals 0.1 mL samples of reaction mixture were collected to which one drop of ethyl vinyl ether was added to deactivate the catalyst. Conversion reaction as a function of time was determined by GC analysis. A summary is presented in Table 2.

(161) TABLE-US-00002 TABLE 2 DEDAM conversion with intermediate 5a as a function of time. Time Conversion (%) (min) 5a 5a + CuCl 15 7 >99 30 10 — 60 27 — 120 78 — 240 88 — 360 95 —

Example XXIII

(162) Application of Precatalysts 1a-1j in Ethenolysis Reactions of Fatty Acid Methyl Esters which were Obtained by Rapeseed Oil Transesterification (MOR).

(163) ##STR00052##

(164) To the reaction, a mixture of fatty acid methyl esters which were obtained by rapeseed oil transesterification (MOR), was used, composed of: about 61% methyl oleate, about 21% linoleic acid methyl ester, about 10% α-linolenic acid ester, about 7% saturated fatty acid methyl esters including about 4% methyl palmitate and about 2% methyl stearate.

(165) To degassed MOR (610 g) cooled to 0° C. a solution of catalyst (0.052 mmol) in dry deoxygenated toluene (5 mL) was added. The mixture was vacuum-pumped to an autoclave and stirred for 2 hours at 30° C. at 10 bar of ethylene. After 2 hours the reaction was quenched and to the reaction mixture 6 mL 0.1 M solution of SnachCat [CAS: 51641-96-4] was added to deactivate the catalyst.

(166) ##STR00053##

(167) The samples were analyzed using gas chromatography. The conversion was determined using methyl palmitate as an internal standard.

(168) Reaction mixtures obtained in reactions catalysed with 1d and 1e after filtration through short pad of silica gel were distilled under reduced pressure, giving 173 g and 179 g of 9-decenoic acid methyl ester (9-DAME), respectively.

(169) Conversion and percentage (GC peak area) of 9-decenoic acid methyl ester (9-DAME) were given in the Table 3.

(170) TABLE-US-00003 TABLE 3 MOR conversion in ethenolysis reaction with precatalysts 1a-1i Isolated Conversion Percentage of 9-DAME (%) in the 9-DAME Precatalyst (%) reaction mixture based on GC (g) 1a 77 25 — 1b 71 23 — 1c 69 21 — 1d 83 31 173 1e 79 29 179 1j 27  8 — 1i 21 5 (reaction conducted at 40° C.) —
Analytical Data Obtained for 9-DAME:

(171) .sup.1H NMR (CDCl.sub.3, 500 MHz): δ=5.79 (ddt, J=17.0; 10.2; 6.7 Hz, 1H), 4.98 (dq, J=17.1; 1.7 Hz, 1H), 4.92 (ddd, J=11.4; 2.3; 1.2 Hz, 1H), 3.66 (s, 3H), 2.29 (t, J=7.5 Hz, 2H), 2.06-1.99 (m, 2H), 1.66-1.56 (m, 2H), 1.40-1.24 (m, 8H) ppm.

(172) .sup.13C NMR (CDCl.sub.3, 125 MHz): 174.3, 139.1, 114.2, 51.4, 34.1, 33.7, 29.1, 28.9, 28.8, 24.9 ppm.

Example XXIV

(173) Preparation Method of Intermediate 5c from Precursor M10 and CAAC Salt 3ad.

(174) ##STR00054##

(175) To salt 3ad (6.00 g, 14.73 mmol, 3 molar equivalents) in argon atmosphere dry deoxygenated toluene (35 mL) was added. The mixture was heated to 80° C. and solution of LiHMDS in toluene (1 M, 14.73 mL, 14.73 mmol, 3 molar equivalents) was added. After 1 minute solid complex M10 (4.35 g, 4.91 mmol, 1 molar equivalent) was added. After 2 minutes the mixture was cooled down to the room temperature. Triethylamine (2 mL) was added and filtrated through a short pad of silica gel (deactivated with triethylamine), which was washed with 100 mL toluene/triethylamine mixture (95:5 v/v). Solvents were evaporated under reduced pressure. The crude product was isolated by column chromatography on silica gel (deactivated with triethylamine; eluent: from cyclohexane/triethylamine (95:5 v/v) to cyclohexane/ethyl acetate/triethylamine (90:5:5 v/v/v)). Red brown fraction was collected and concentrated to dryness. The residue was dissolved in n-pentane. Solvent was evaporated to 25% of its original amount-precipitate formed during evaporation was filtrated off, washed with a minimal amount of cold n-pentane and dried under high vacuum giving an orange brown crystalline solid-compound 5c (1.73 g, 35%).

(176) .sup.1H NMR (C.sub.6D.sub.6, 500 MHz): δ=9.59 (d, J=7.5 Hz, 1H), 8.06 (d, J=7.7 Hz, 2H), 7.76 (d, J=7.4 Hz, 2H), 7.49-7.43 (m, 3H), 7.42-7.37 (m, 2H), 7.37-7.23 (m, 6H), 7.22-7.06 (m, 5H), 7.01-6.97 (m, 1H), 6.88 (t, J=7.3 Hz, 1H), 6.81 (d, J=7.6 Hz, 1H), 6.64 (t, J=7.6 Hz, 1H), 6.34 (d, J=7.5 Hz, 1H), 4.14 (dq, J=14.9; 7.2 Hz, 1H), 3.10-2.83 (m, 4H), 2.83-2.73 (m, 1H), 2.73-2.63 (m, 1H), 2.57-2.48 (m, 1H), 2.05 (d, J=12.3 Hz, 1H), 1.94-1.89 (m, 1H), 1.84 (d, J=12.7 Hz, 1H), 1.78 (s, 3H), 1.62 (d, J=12.7 Hz, 1H), 1.48-1.40 (m, 6H), 1.03 (dt, J=14.5; 7.3 Hz, 6H), 0.95 (dt, J=14.5; 7.3 Hz, 3H), 0.77 (s, 3H), 0.71 (s, 3H), 0.63 (s, 3H), 0.50 (s, 3H) ppm.

(177) .sup.13C NMR (CD.sub.2Cl.sub.2, 125 MHz): δ=288.1, 279.5, 273.4, 263.3, 150.5, 148.9, 148.1, 147.8, 147.2, 146.6, 144.9, 143.8, 143.8, 143.3, 142.0, 141.6, 141.4, 140.5, 140.2, 139.0, 138.9, 138.6, 138.1, 137.9, 137.5, 136.6, 135.9, 135.0, 131.0, 130.7, 130.4, 130.0, 129.9, 129.7, 129.2, 128.8, 128.7, 128.2, 128.1, 127.8, 127.7, 127.6, 127.5, 127.4, 127.3, 127.3, 127.2, 127.2, 127.2, 127.0, 126.9, 126.8, 126.6, 126.5, 126.4, 126.3, 126.3, 126.1, 125.4, 125.0, 124.7, 118.7, 116.5, 115.7, 96.2, 81.5, 80.5, 79.0, 68.9, 66.0, 65.1, 57.1, 55.4, 52.1, 49.1, 44.4, 32.2, 31.5, 30.2, 29.7, 29.4, 29.1, 28.6, 28.0, 27.7, 27.6, 27.3, 27.2, 26.6, 25.7, 25.5, 24.8, 24.8, 24.4, 16.3, 16.1, 14.5, 14.4, 14.0, 13.6, 13.4, 12.4 ppm.

(178) HRMS-ESI calculated for C.sub.61H.sub.68N.sub.2Cl.sub.2Ru [M.].sup.+: 1000.3803; found 1000.3798.

(179) Elemental analysis: calculated for C.sub.61H.sub.68N.sub.2Cl.sub.2Ru:

(180) C, 73.18; H, 6.85; N, 2.80; Cl, 7.08; found: C, 73.14; H, 7.00; N, 2.95; Cl, 7.10.

Example XXV

(181) Preparation Method of Intermediate 5d from Precursor M10 and CAAC Salt 3ae.

(182) ##STR00055##

(183) To salt 3ae (2.36 g, 6.0 mmol, 3 molar equivalents) dry deoxygenated toluene (14 mL) was added in argon atmosphere. The mixture was heated to 80° C. and solution of LiHMDS in toluene (1 M, 6.0 mL, 6.0 mmol, 3 molar equivalents) was added. After 1 minute solid complex M10 (1.77 g, 2.0 mmol, 1 molar equivalent) was added. After 2 minutes the mixture was cooled down to the room temperature. Triethylamine (2 mL) was added and filtrated through a short pad of silica gel (deactivated with triethylamine), which was washed with 50 mL toluene/triethylamine mixture (95:5 v/v). Solvents were evaporated under reduced pressure. The crude product was isolated by column chromatography on silica gel (deactivated with triethylamine; eluent: from cyclohexane/triethylamine (95:5 v/v) to cyclohexane/ethyl acetate/triethylamine (90:5:5 v/v/v)). Red brown fraction was collected and concentrated to dryness. The residue was dissolved in n-pentane. Solvent was evaporated to 25% of its original amount-precipitate formed during evaporation was filtrated off, washed with a minimal amount of cold n-pentane and dried under high vacuum giving an orange brown crystalline solid-compound 5d (0.345 g, 18%).

(184) .sup.1H NMR (C.sub.6D.sub.6, 500 MHz): δ=9.69-9.49 (m, 1H), 8.17-7.99 (m, 2H), 7.82-7.65 (m, 2H), 7.60-7.23 (m, 9H), 7.23-7.04 (m, 6H), 7.02-6.10 (m, 6H), 3.14-2.76 (m, 4H), 2.74-2.46 (m, 2H), 2.38-2.24 (m, 3H), 2.10-1.35 (m, 12H), 1.31-1.23 (m, 2H), 1.08-0.92 (m, 5H), 0.80-0.59 (m, 10H) ppm.

(185) .sup.13C NMR (C.sub.6D.sub.6, 125 MHz): δ=290.2, 289.9, 289.0, 288.6, 280.9, 279.2, 279.1, 274.5, 274.2, 274.0, 149.4, 149.3, 149.3, 149.2, 149.0, 148.3, 145.3, 145.3, 145.2, 144.4, 144.2, 144.1, 144.1, 142.4, 142.1, 141.9, 141.8, 141.8, 141.1, 140.9, 139.6, 139.4, 139.2, 139.1, 139.0, 138.8, 138.6, 138.2, 138.1, 138.1, 136.9, 136.6, 136.0, 136.0, 135.7, 135.6, 135.5, 135.2, 131.1, 131.0, 130.9, 130.8, 130.7, 130.6, 130.4, 130.3, 130.1, 130.0, 129.9, 129.7, 129.6, 129.5, 129.1, 129.1, 129.0, 128.7, 128.3, 128.0, 127.9, 127.8, 127.8, 127.7, 127.7, 127.7, 127.6, 127.6, 127.3, 127.2, 126.8, 126.8, 126.7, 126.5, 126.3, 124.8, 124.6, 116.9, 116.9, 81.7, 81.5, 81.1, 80.9, 80.7, 69.1, 69.0, 65.4, 65.3, 65.2, 56.8, 56.7, 56.6, 55.5, 55.1, 53.9, 53.6, 31.0, 30.7, 30.2, 29.9, 29.9, 29.6, 29.6, 29.5, 29.3, 29.2, 29.0, 28.0, 27.9, 27.6, 27.4, 27.4, 27.3, 27.1, 25.8, 25.5, 25.4, 25.2, 25.1, 25.1, 25.0, 24.2, 24.0, 22.7, 22.6, 14.9, 14.8, 14.0, 13.8, 12.6, 12.6 ppm.

(186) HRMS-ESI: calculated for C.sub.59H.sub.64N.sub.2Cl.sub.2Ru [M.].sup.+: 972.3490; found 972.3475.

(187) Elemental analysis: calculated for C.sub.59H.sub.64N.sub.2Cl.sub.2Ru:

(188) C, 72.82; H, 6.63; N, 2.88; Cl, 7.29; found: C, 72.69; H, 6.68; N, 2.71; Cl, 7.07.

Example XXVI

(189) Preparation Method of Intermediate 5e from Precursor M10 and CAAC Salt 3ab.

(190) ##STR00056##

(191) To salt 3ab (8.29 g, 24.0 mmol, 3 molar equivalents) dry deoxygenated toluene (56 mL) was added in argon atmosphere. The mixture was heated to 80° C. and solution of LiHMDS in toluene (1 M, 24.0 mL, 24.0 mmol, 3 molar equivalents) was added. After 1 minute solid complex M10 (7.09 g, 8.0 mmol, 1 molar equivalent) was added. After 2 minutes the mixture was cooled down to the room temperature. Triethylamine (5 mL) was added and filtrated through a short pad of silica gel (deactivated with triethylamine), which was washed with 75 mL toluene/triethylamine mixture (95:5 v/v). Solvents were evaporated under reduced pressure. The crude product was isolated by column chromatography on silica gel (deactivated with triethylamine; eluent: from cyclohexane/triethylamine (95:5 v/v) to cyclohexane/ethyl acetate/triethylamine (90:5:5 v/v/v)). Red brown fraction was collected and concentrated to dryness. The residue was dissolved in n-pentane. Solvent was evaporated to 25% of its original amount-precipitate formed during evaporation was filtrated off, washed with a minimal amount of cold n-pentane and dried under high vacuum giving an orange brown crystalline solid-compound 5e (2.89 g, 41%).

(192) .sup.1H NMR (C.sub.6D.sub.6, 500 MHz): δ=10.05-8.65 (m, 1H), 8.50-7.45 (m, 3H), 7.40-7.15 (m, 7H), 7.05-6.05 (m, 5H), 3.86-3.62 (m, 1H), 3.12-2.89 (m, 1H), 2.86-2.02 (m, 8H), 1.92-1.11 (m, 22H), 1.10-0.65 (m, 14H), 0.44 (s, 2H) ppm.

(193) .sup.13C NMR (CD.sub.2Cl.sub.2, 125 MHz): δ=281.7, 281.0, 280.1, 279.1, 278.5, 147.6, 146.3, 142.0, 141.8, 141.1, 140.9, 139.9, 139.8, 139.5, 137.7, 136.7, 136.4, 136.1, 134.0, 131.8, 130.7, 130.0, 129.8, 129.5, 129.4, 129.2, 129.0, 128.7, 127.5, 127.3, 127.2, 127.0, 126.6, 125.8, 125.4, 116.6, 116.5, 80.3, 80.3, 62.7, 61.9, 61.4, 57.3, 56.8, 56.0, 32.0, 31.4, 30.8, 30.0, 28.9, 28.8, 28.6, 28.4, 27.8, 27.5, 27.3, 26.9, 26.5, 26.4, 25.7, 25.4, 24.0, 23.8, 23.2, 22.7 ppm.

(194) HRMS-ESI calculated for C.sub.51H.sub.64N.sub.2Cl.sub.2Ru [M.].sup.+: 876.3490; found 876.3477.

(195) Elemental analysis: calculated for C.sub.51H.sub.64N.sub.2Cl.sub.2Ru:

(196) C, 69.84; H, 7.36; N, 3.19; Cl, 8.08; found: C, 69.94; H, 7.43; N, 3.14; Cl, 8.17.

Example XXVII

(197) Preparation Method of Intermediate 5e from Precursor M1 and CAAC Salt 3ab.

(198) ##STR00057##

(199) To salt 3ab (1.04 g, 3.0 mmol, 3 molar equivalents) dry deoxygenated toluene (7 mL) was added in argon atmosphere. The mixture was heated to 80° C. and solution of LiHMDS in toluene (1 M, 3.0 mL, 3.0 mmol, 3 molar equivalents) was added. After 1 minute solid complex M1 (0.923 g, 1.0 mmol, 1 molar equivalent) was added. After 10 minutes the mixture was cooled down to the room temperature. Triethylamine (1 mL) was added and filtrated through a short pad of silica gel (deactivated with triethylamine), which was washed with 25 mL toluene/triethylamine mixture (95:5 v/v). Solvents were evaporated under reduced pressure. The crude product was isolated by column chromatography on silica gel (deactivated with triethylamine; eluent: from cyclohexane/triethylamine (95:5 v/v) to cyclohexane/ethyl acetate/triethylamine (90:5:5 v/v/v)). Red brown fraction was collected and concentrated to dryness. The residue was dissolved in n-pentane. Solvent was evaporated to 25% of its original amount-precipitate formed during evaporation was filtrated off, washed with a minimal amount of cold n-pentane and dried under high vacuum giving an orange brown crystalline solid-compound 5e (0.72 g, 82%).

(200) Analytical data for compound 5e obtained in this Example were identical as in Example XXVI.

Example XXVIII

(201) Preparation Method of Intermediate 5f from Precursor M10 and CAAC Salt 3af.

(202) ##STR00058##

(203) To salt 3af (2.36 g, 6.0 mmol, 3 molar equivalents) dry deoxygenated toluene (14 mL) was added in argon atmosphere. The mixture was heated to 80° C. and solution of LiHMDS in toluene (1 M, 6.0 mL, 6.0 mmol, 3 molar equivalents) was added. After 1 minute solid complex M10 (1.77 g, 2.0 mmol, 1 molar equivalent) was added. After 2 minutes the mixture was cooled down to the room temperature. Triethylamine (2 mL) was added and filtrated through a short pad of silica gel (deactivated with triethylamine), which was washed with 50 mL toluene/triethylamine mixture (95:5 v/v). Solvents were evaporated under reduced pressure. The crude product was isolated by column chromatography on silica gel (deactivated with triethylamine; eluent: from cyclohexane/triethylamine (95:5 v/v) to cyclohexane/ethyl acetate/triethylamine (90:5:5 v/v/v)). Red brown fraction was collected and concentrated to dryness. The residue was dissolved in n-pentane. Solvent was evaporated to 25% of its original amount-precipitate formed during evaporation was filtrated off, washed with a minimal amount of cold n-pentane and dried under high vacuum giving an orange brown crystalline solid-compound 5f (0.210 g, 11%).

(204) .sup.1H NMR (C.sub.6D.sub.6, 500 MHz): δ=9.57 (d, J=7.6 Hz, 1H), 8.14 (d, J=7.8 Hz, 2H), 7.73 (d, J=7.6 Hz, 2H), 7.61 (s, 1H), 7.52 (d, J=7.5 Hz, 2H), 7.44 (t, J=7.6 Hz, 2H), 7.37-7.16 (m, 5H), 7.15-7.11 (m, 1H), 7.08-6.80 (m, 5H), 6.64 (s, 1H), 6.42 (s, 1H), 5.90 (s, 1H), 2.85 (s, 3H), 2.32 (s, 6H), 2.22 (s, 3H), 2.19 (s, 3H), 2.10 (d, J=12.5 Hz, 1H), 1.95-1.84 (m, 2H), 1.77 (s, 3H), 1.70 (s, 3H), 1.64 (d, J=12.7 Hz, 1H), 1.50 (s, 3H), 0.80 (s, 3H), 0.72 (s, 3H), 0.67 (s, 3H), 0.61 (s, 3H) ppm.

(205) .sup.13C NMR (CD.sub.2Cl.sub.2, 125 MHz): δ=286.8, 278.5, 272.1, 148.7, 147.8, 144.8, 141.2, 139.1, 138.8, 138.5, 138.2, 137.7, 137.6, 136.6, 136.1, 136.0, 135.2, 134.3, 131.7, 131.0, 130.3, 130.2, 129.8, 129.6, 128.8, 128.6, 128.1, 127.5, 127.3, 127.3, 127.0, 126.6, 126.4, 116.0, 82.0, 81.9, 68.8, 65.0, 57.0, 55.6, 30.39, 30.16, 29.55, 28.50, 27.86, 27.37, 24.64, 24.30, 21.91, 21.13, 21.0 ppm.

(206) HRMS-ESI calculated for C.sub.59H.sub.64N.sub.2Cl.sub.2Ru [M.].sup.+: 972.3490; found 972.3483.

(207) Elemental analysis: calculated for C.sub.59H.sub.64N.sub.2Cl.sub.2Ru:

(208) C, 72.82; H, 6.63; N, 2.88; Cl, 7.29; found: C, 72.88; H, 6.78; N, 2.71; Cl, 7.16.

Example XXIX

(209) Preparation Method of Intermediate 5 g from Precursor M10 and CAAC Salt 3ag.

(210) ##STR00059##

(211) To salt 3ag (1.99 g, 6.0 mmol, 3 molar equivalents) dry deoxygenated toluene (14 mL) was added in argon atmosphere. The mixture was heated to 80° C. and solution of LiHMDS in toluene (1 M, 6.0 mL, 6.0 mmol, 3 molar equivalents) was added. After 1 minute, solid complex M10 (1.77 g, 2.0 mmol, 1 molar equivalent) was added. After 2 minutes the mixture was cooled down to the room temperature. Triethylamine (2 mL) was added and filtrated through a short pad of silica gel (deactivated with triethylamine), which was washed with 50 mL toluene/triethylamine mixture (95:5 v/v). Solvents were evaporated under reduced pressure. The crude product was isolated by column chromatography on silica gel (deactivated with triethylamine; eluent: from cyclohexane/triethylamine (95:5 v/v) to cyclohexane/ethyl acetate/triethylamine (90:5:5 v/v/v)). Red brown fraction was collected and concentrated to dryness. The residue was dissolved in n-pentane. Solvent was evaporated to 25% of its original amount-precipitate formed during evaporation was filtrated off, washed with a minimal amount of cold n-pentane and dried under high vacuum giving an orange brown crystalline solid-compound 5g (0.561 g, 33%).

(212) .sup.1H NMR (CD.sub.2Cl.sub.2, 500 MHz): δ=8.51 (d, J=7.6 Hz, 1H), 7.75-7.65 (m, 2H), 7.52-7.46 (m, 1H), 7.46-7.39 (m, 2H), 7.14 (s, 1H), 7.11-7.04 (m, 1H), 7.03-6.96 (m, 1H), 6.84 (dd, J=7.2; 1.4 Hz, 1H), 6.23 (s, 2H), 5.79 (s, 2H), 2.16 (s, 6H), 2.11 (s, 6H), 2.06-2.03 (m, 10H), 1.86 (s, 6H), 1.72 (s, 6H), 1.18 (s, 6H), 1.12 (s, 6H) ppm.

(213) .sup.13C NMR (CD.sub.2Cl.sub.2, 125 MHz): δ=280.2, 277.9, 144.0, 140.7, 138.2, 137.9, 137.4, 136.4, 135.8, 135.4, 134.1, 129.7, 129.6, 129.3, 129.2, 127.3, 127.0, 126.6, 126.6, 115.5, 80.9, 56.9, 54.5, 32.3, 32.1, 30.2, 29.5, 21.6, 21.4, 21.0 ppm.

(214) HRMS-ESI calculated for C.sub.49H.sub.60N.sub.2Cl.sub.2Ru [M.].sup.+: 848.3177; found 848.3161.

(215) Elemental analysis: calculated for C.sub.49H.sub.60N.sub.2Cl.sub.2Ru:

(216) C, 69.32; H, 7.12; N, 3.30; Cl, 8.35; found: C, 69.40; H, 7.03; N, 3.22; Cl, 8.56.

Example XXX

(217) Preparation Method of Intermediate 5 g and Minor Compound 6g from Precursor M1 and CAAC Salt 3ag.

(218) ##STR00060##

(219) To salt 3ag (1.99 g, 6.0 mmol, 3 molar equivalents) dry deoxygenated toluene (14 mL) was added in argon atmosphere. The mixture was heated to 80° C. and solution of LiHMDS in toluene (1 M, 6.0 mL, 6.0 mmol, 3 molar equivalents) was added. After 1 minute solid complex M1 (1.85 g, 2.0 mmol, 1 molar equivalent) was added. After 30 minutes the mixture was cooled down to the room temperature. Triethylamine (2 mL) was added and filtrated through a short pad of silica gel (deactivated with triethylamine), which was washed with 50 mL toluene/triethylamine mixture (95:5 v/v). Solvents were evaporated under reduced pressure. Crude products 5 g and 6 g were isolated by column chromatography on silica gel (deactivated with triethylamine; eluent: from cyclohexane/triethylamine (95:5 v/v) to cyclohexane/ethyl acetate/triethylamine (90:5:5 v/v/v)). Two red brown fractions were collected and concentrated to dryness. First fraction residue was dissolved in n-pentane. Solvent was evaporated to 25% of its original amount-precipitate formed during evaporation was filtrated off, washed with a minimal amount of cold n-pentane and dried under high vacuum giving an orange brown crystalline solid-compound 6g (0.270 g, 15%). Second fraction residue was dissolved in n-pentane. Solvent was evaporated to 25% of its original amount-precipitate formed during evaporation was filtrated off, washed with a minimal amount of cold n-pentane and dried under high vacuum giving an orange brown crystalline solid-compound 5g (0.350 g, 21%).

(220) Analytical data for compound 5g obtained in this Example were identical as in Example XXIX.

(221) Analytical data for compound 6g:

(222) .sup.1H NMR (CD.sub.2Cl.sub.2, 500 MHz): δ=8.61 (d, J=7.3 Hz, 1H), 7.70 (dd, J=8.2; 1.4 Hz, 2H), 7.54-7.47 (m, 1H), 7.42 (t, J=7.6 Hz, 2H), 7.30 (s, 1H), 7.24-7.18 (m, 1H), 7.17-7.11 (m, 1H), 7.06-7.01 (m, 1H), 6.39 (s, 1H), 6.01 (s, 1H), 2.50-2.38 (m, 3H), 2.31 (s, 3H), 2.17 (s, 3H), 2.14 (d, J=1.8 Hz, 2H), 2.06 (s, 3H), 2.00 (s, 3H), 1.93 (s, 3H), 1.90-1.80 (m, 3H), 1.76-1.54 (m, 12H), 1.53-1.34 (m, 6H), 1.22 (s, 6H), 1.20-1.06 (m, 9H) ppm.

(223) .sup.13C NMR (CD.sub.2Cl.sub.2, 125 MHz): δ=287.7, 287.7, 274.7, 274.2, 144.8, 141.4, 138.3, 137.4, 137.3, 137.3, 136.9, 136.5, 136.2, 130.0, 129.9, 129.6, 129.5, 128.1, 128.1, 127.8, 126.8, 116.5, 80.3, 80.3, 57.5, 57.4, 53.5, 53.5, 36.1, 35.6, 32.8, 32.7, 31.9, 31.6, 30.4, 30.1, 29.9, 28.8, 28.6, 28.5, 28.4, 28.3, 27.6, 27.5, 27.2, 27.1, 26.9, 26.9, 26.8, 22.9, 21.7, 21.4, 21.2 ppm.

(224) .sup.31P NMR (CD.sub.2Cl.sub.2, 202 MHz): δ=28.7 ppm.

(225) HRMS-ESI calculated for C.sub.50H.sub.68NCl.sub.2RuP [M.].sup.+: 885.3510; found 885.3506.

(226) Elemental analysis: calculated for C.sub.50H.sub.68Cl.sub.2NPRu:

(227) C, 67.78; H, 7.74; N, 1.58; Cl, 8.00; found: C, 67.84; H, 7.67; N, 1.47; Cl, 7.91.

Example XXXI

(228) Preparation Method of Intermediate 5h from Precursor M10 and CAAC Salt 3ah.

(229) ##STR00061##

(230) To salt 3ah (1.99 g, 6.0 mmol, 3 molar equivalents) dry deoxygenated toluene (14 mL) was added in argon atmosphere. The mixture was heated to 80° C. and solution of LiHMDS in toluene (1 M, 6.0 mL, 6.0 mmol, 3 molar equivalents) was added. After 1 minute solid complex M10 (1.77 g, 2.0 mmol, 1 molar equivalent) was added. After 2 minutes the mixture was cooled down to the room temperature. The crude product was isolated by column chromatography on silica gel (eluent: cyclohexane/ethyl acetate (9:1 v/v)). Red brown fraction was collected and concentrated to dryness. The residue was dissolved in a small amount of methylene chloride and excess of methanol was added. Methylene chloride was removed under reduced pressure-precipitate formed during evaporation was filtrated off, washed with a minimal amount of cold methanol and dried under high vacuum giving an orange brown crystalline solid-compound 5h (0.589 g, 35%).

(231) .sup.1H NMR (C.sub.6D.sub.6, 500 MHz): δ=9.88-8.08 (m, 1H), 8.02-7.40 (m, 3H), 7.39-7.20 (m, 4H), 7.12-6.85 (m, 3H), 6.75-6.10 (m, 5H), 3.85-2.90 (m, 2H), 2.87-2.67 (m, 1H), 2.66-2.50 (m, 1H), 2.46-2.22 (m, 12H), 2.21-2.01 (m, 3H), 1.80-1.15 (m, 7H), 1.14-0.65 (m, 18H) ppm.

(232) .sup.13C NMR (CD.sub.2Cl.sub.2, 125 MHz): δ=280.4, 280.3, 277.9, 277.8, 277.6, 144.2, 144.1, 141.1, 141.0, 140.9, 139.5, 139.4, 139.1, 139.1, 138.8, 137.9, 137.8, 137.8, 137.4, 135.5, 135.0, 134.6, 134.5, 131.0, 130.5, 129.7, 129.3, 129.2, 129.1, 129.0, 128.7, 128.4, 127.8, 127.7, 127.4, 127.3, 127.0, 126.8, 126.7, 126.6, 126.5, 125.2, 124.3, 116.3, 116.2, 116.1, 81.9, 80.6, 80.5, 61.5, 57.0, 56.9, 56.5, 54.9, 54.8, 54.7, 54.6, 32.7, 32.4, 32.4, 32.0, 31.8, 31.0, 30.2, 29.6, 29.5, 29.1, 28.8, 27.4, 25.2, 25.1, 24.6, 22.1, 21.8, 14.7, 13.1, 12.7 ppm.

(233) HRMS-ESI calculated for C.sub.49H.sub.60N.sub.2Cl.sub.2Ru [M.].sup.+: 848.3177; found 848.3159.

(234) Elemental analysis: calculated for C.sub.49H.sub.60N.sub.2Cl.sub.2Ru: C, 69.32; H, 7.12; N, 3.30; Cl, 8.35; found: C, 69.15; H, 7.30; N, 3.48; Cl, 8.40.

Example XXXII

(235) Preparation Method of Intermediate 5i from Precursor M10 and CAAC Salt 3ai.

(236) ##STR00062##

(237) To salt 3ai (0.847 g, 2.0 mmol, 2 molar equivalents) dry deoxygenated toluene (8 mL) was added in argon atmosphere. The mixture was heated to 80° C. and solution of LiHMDS in toluene (1 M, 2.0 mL, 2.0 mmol, 2 molar equivalents) was added. After 1 minute solid complex M10 (0.887 g, 1.0 mmol, 1 molar equivalent) was added. After 2 minutes the mixture was cooled down to the room temperature. Triethylamine (1 mL) was added and filtrated through a short pad of silica gel (deactivated with triethylamine), which was washed with 50 mL toluene/triethylamine mixture (95:5 v/v). Solvents were evaporated under reduced pressure. The crude product was isolated by column chromatography on silica gel (deactivated with triethylamine; eluent: from cyclohexane/triethylamine (95:5 v/v) to cyclohexane/ethyl acetate/triethylamine (90:5:5 v/v/v)). Red brown fraction was collected and concentrated to dryness. The residue was dissolved in n-pentane. Solvent was evaporated to 25% of its original amount-precipitate formed during evaporation was filtrated off, washed with a minimal amount of cold n-pentane and dried under high vacuum giving an orange brown crystalline solid-compound 5i (0.147 g, 14%) as a mixture of isomers (isomer A-major and isomer B-minor). The filtrate was evaporated to dryness. It was dissolved in a small amount of methylene chloride and excess of methanol was added. Methylene chloride was evaporated under reduced pressure-precipitate formed during evaporation was filtrated off, washed with a minimal amount of cold methanol and dried under high vacuum giving red crystalline solid-compound 5i (0.184 g, 18%) as a mixture of isomers (isomer A-minor and isomer B-major).

(238) .sup.1H NMR (C.sub.6D.sub.6, 500 MHz): δ=9.86-8.38 (m, 1H), 8.35-7.65 (m, 6H), 7.62-7.53 (m, 1H), 7.51-7.45 (m, 1H), 7.44-7.37 (m, 1H), 7.35-7.25 (m, 5H), 7.10-6.55 (m, 5H), 4.04-3.72 (m, 1H), 3.45-2.75 (m, 3H), 2.08-1.94 (m, 3H), 1.65-1.05 (m, 35H), 0.98-0.71 (m, 14H) ppm (mixture of isomers).

(239) .sup.13C NMR (CD.sub.2Cl.sub.2, 125 MHz): δ=282.3, 281.1, 280.2, 279.0, 278.9, 277.5, 145.9, 145.3, 144.5, 144.5, 144.4, 142.8, 142.4, 141.2, 140.6, 140.2, 138.0, 137.5, 135.0, 134.7, 134.4, 134.4, 134.2, 133.2, 132.8, 132.6, 132.6, 132.5, 132.4, 132.4, 132.2, 131.8, 131.8, 131.4, 131.2, 130.6, 130.5, 129.5, 129.4, 129.2, 129.1, 129.0, 128.9, 128.7, 128.4, 128.0, 127.9, 127.6, 127.5, 127.4, 127.3, 127.2, 127.2, 127.1, 126.9, 126.2, 126.0, 125.7, 125.7, 125.6, 125.4, 125.2, 125.1, 124.7, 123.7, 123.6, 116.1, 115.6, 115.3, 81.5, 81.3, 80.8, 80.1, 62.0, 61.5, 56.5, 56.2, 55.8, 55.3, 54.8, 35.5, 35.4, 35.0, 34.3, 33.2, 32.2, 32.2, 31.6, 31.5, 31.3, 31.3, 30.8, 30.7, 30.6, 30.6, 30.5, 30.5, 30.4, 30.2, 30.1, 30.0, 29.9, 29.7, 29.5, 29.5, 28.9, 28.9, 28.8, 28.7, 28.3, 27.6, 27.5, 27.3, 26.8, 26.2, 26.0, 25.7, 25.7, 25.4, 24.9, 24.8, 24.7, 24.6, 24.5, 24.4, 24.3, 24.2, 23.8, 23.3, 23.2, 23.1, 23.1, 23.0, 22.9, 22.5 ppm.

(240) Analytical Data for Isomer A-Enriched Mixture:

(241) HRMS-ESI calculated for C.sub.63H.sub.76N.sub.2Cl.sub.2Ru [M.].sup.+: 1032.4429; found 1032.4402.

(242) Elemental analysis: calculated for C.sub.63H.sub.76N.sub.2Cl.sub.2Ru:

(243) C, 73.23; H, 7.41; N, 2.71; Cl, 6.86; found: C, 73.19; H, 7.46; N, 2.60; Cl, 6.84.

(244) Analytical Data for Isomer B-Enriched Mixture:

(245) HRMS-ESI calculated for C.sub.63H.sub.76N.sub.2Cl.sub.2Ru [M.].sup.+: 1032.4429; found 1032.4426.

(246) Elemental analysis: calculated for C.sub.63H.sub.76N.sub.2Cl.sub.2Ru:

(247) C, 73.23; H, 7.41; N, 2.71; Cl, 6.86; found: C, 73.16; H, 7.31; N, 2.74; Cl, 6.97.

Example XXXIII

(248) Preparation Method of Intermediate 5j from Precursor Gru-I and CAAC Salt 3ab.

(249) ##STR00063##

(250) To salt 3ab (1.04 g, 3.0 mmol, 3 molar equivalents) dry deoxygenated toluene (7 mL) was added in argon atmosphere. The mixture was heated to 80° C. and solution of LiHMDS in toluene (1 M, 3.0 mL, 3.0 mmol, 3 molar equivalents) was added. After 1 minute solid complex Gru-I (0.823 g, 1.0 mmol, 1 molar equivalent) was added. After 2 minutes the mixture was cooled down to the room temperature. Triethylamine (1 mL) was added and filtrated through a short pad of silica gel (deactivated with triethylamine), which was washed with 25 mL toluene/triethylamine mixture (95:5 v/v). Solvents were evaporated under reduced pressure. The crude product was isolated by column chromatography on silica gel (deactivated with triethylamine; eluent: from cyclohexane/triethylamine (95:5 v/v) to cyclohexane/ethyl acetate/triethylamine (90:5:5 v/v/v)). Brown fraction was collected and concentrated to dryness. The residue was dissolved in n-pentane. Solvent was evaporated to 25% of its original amount-precipitate formed during evaporation was filtrated off, washed with a minimal amount of cold n-pentane and dried under high vacuum giving dark brown crystalline solid-compound 5j (0.441 g, 57%).

(251) .sup.1H NMR (C.sub.6D.sub.6, 500 MHz): δ=18.29 (s, 1H), 9.41 (d, J=8.1 Hz, 1H), 7.12-7.07 (m, 1H), 7.01-6.95 (m, 1H), 6.84 (dd, J=7.9; 1.6 Hz, 2H), 6.67 (td, J=7.6; 1.5 Hz, 1H), 6.42 (t, J=7.7 Hz, 2H), 6.22 (d, J=7.9 Hz, 1H), 5.93 (dd, J=7.5; 1.6 Hz, 2H), 3.23 (hept, J=6.4 Hz, 2H), 2.31 (d, J=4.1 Hz, 12H), 2.21 (s, 6H), 1.74-1.60 (m, 10H), 1.18 (s, 6H), 1.11 (d, J=6.6 Hz, 6H), 0.73 (s, 6H) ppm (main isomer).

(252) .sup.13C NMR (CD.sub.2Cl.sub.2, 125 MHz): δ=285.0, 284.9, 281.5, 149.4, 145.3, 139.1, 136.8, 131.9, 130.9, 129.1, 128.3, 127.6, 127.5, 127.3, 124.5, 79.3, 56.5, 55.2, 32.8, 31.8, 31.1, 29.8, 28.9, 28.5, 28.4, 28.3, 26.8, 22.2 ppm.

(253) HRMS-ESI calculated for C.sub.43H.sub.60N.sub.2Cl.sub.2Ru [M.].sup.+: 776.3177; found 776.3140.

(254) Elemental analysis: calculated for C.sub.43H.sub.60N.sub.2Cl.sub.2Ru:

(255) C, 66.47; H, 7.78; N, 3.61; Cl, 9.13; found: C, 66.24; H, 7.75; N, 3.46; Cl, 9.01.

Example XXXIV

(256) Preparation Method of Precatalyst 1k from Precursor M10 and CAAC Salt 3aj.

(257) ##STR00064##

(258) To salt 3aj (0.331 g, 1.0 mmol, 2 molar equivalents) dry deoxygenated toluene (4 mL) was added in argon atmosphere. The mixture was heated to 80° C. and solution of LiHMDS in toluene (1 M, 1.0 mL, 1.0 mmol, 2 molar equivalents) was added. After 1 minute solid complex M10 (0.443 g, 0.5 mmol, 1 molar equivalent) was added. After 2 minutes the mixture was cooled down to 60° C. Benzylidene ligand 4a (0.106 g, 0.6 mmol, 1.2 molar equivalents) and CuCl (0.173 g, 1.75 mmol, 3.5 molar equivalents) were added. The whole was stirred for 20 minutes at 60° C. and cooled down to the room temperature. The crude product was isolated by column chromatography on silica gel (eluent: toluene). Green fraction was collected and concentrated to dryness. The residue was dissolved in ethyl acetate and filtrated. The solvent was evaporated, the residue was washed with isopropanol and dried under high vacuum giving green crystalline solid-precatalyst 1k (0.112 g, 40%).

(259) .sup.1H NMR (CD.sub.2Cl.sub.2, 500 MHz): δ=16.22 (s, 1H), 7.61 (ddd, J=8.2; 7.1; 2.0 Hz, 1H), 7.15 (s, 2H), 7.01-6.89 (m, 3H), 5.16 (hept, J=6.2 Hz, 1H), 2.48 (s, 3H), 2.20 (s, 8H), 2.07 (s, 6H), 1.71 (d, J=6.1 Hz, 6H), 1.41 (s, 6H) ppm.

(260) .sup.13C NMR (CD.sub.2Cl.sub.2, 125 MHz): δ=298.3, 298.1, 266.5, 152.6, 144.9, 139.2, 138.6, 138.2, 131.2, 131.0, 130.9, 123.8, 122.6, 113.6, 79.2, 75.5, 56.5, 52.5, 29.7, 29.3, 22.3, 21.3, 20.9 ppm.

(261) HRMS-ESI calculated for C.sub.27H.sub.37NONaCl.sub.2Ru [M+Na].sup.+: 586.1193; found 586.1185.

(262) Elemental analysis: calculated for C.sub.27H.sub.37NOCl.sub.2Ru:

(263) C, 57.54; H, 6.62; N, 2.49; Cl, 12.58; found: C, 57.51; H, 6.62; N, 2.39; Cl, 12.68.

Example XXXV

(264) Preparation Method of Precatalyst 1l from Precursor M10 and CAAC Salt 3ai.

(265) ##STR00065##

(266) To salt 3ai (1.27 g, 2.0 mmol, 2 molar equivalents) dry deoxygenated toluene (12 mL) was added in argon atmosphere. The mixture was heated to 80° C. and solution of LiHMDS in toluene (1 M, 3.0 mL, 3.0 mmol, 2 molar equivalents) was added. After 1 minute solid complex M10 (1.33 g, 1.0 mmol, 1 molar equivalent) was added. After 2 minutes the mixture was cooled down to 60° C. Benzylidene ligand 4a (0.317 g, 1.8 mmol, 1.2 molar equivalents) and CuCl (0.520 g, 5.25 mmol, 3.5 molar equivalents) were added. The whole was stirred for 10 minutes at 60° C. and cooled down to the room temperature. The crude product was isolated by column chromatography on silica gel (eluent: toluene). Green fraction was collected and concentrated to dryness. The residue was dissolved in ethyl acetate and filtrated. The solvent was evaporated, the residue was washed with isopropanol and dried under high vacuum giving green crystalline solid-precatalyst 11 (0.517 g, 53%).

(267) .sup.1H NMR (CD.sub.2Cl.sub.2, 500 MHz): δ=15.98 (s, 1H), 8.11 (d, J=8.7 Hz, 1H), 7.87-7.84 (m, 1H), 7.81 (d, J=8.4 Hz, 1H), 7.68 (d, J=8.7 Hz, 1H), 7.47 (ddd, J=8.3; 7.4; 1.7 Hz, 1H), 7.35 (dd, J=8.5; 1.7 Hz, 1H), 6.90 (d, J=8.3 Hz, 1H), 6.76 (td, J=7.5; 0.9 Hz, 1H), 6.52 (dd, J=7.6; 1.7 Hz, 1H), 5.12 (hept, J=6.1 Hz, 1H), 3.23 (hept, J=6.6 Hz, 1H), 2.97 (hept, J=6.9 Hz, 1H), 2.38-2.33 (m, 4H), 2.29-2.25 (m, 1H), 2.05 (s, 3H), 1.76 (d, J=6.1 Hz, 3H), 1.66 (d, J=6.1 Hz, 3H), 1.45 (s, 3H), 1.39 (d, J=6.7 Hz, 3H), 1.20 (d, J=6.9 Hz, 6H), 1.17 (s, 3H), 0.80 (d, J=6.5 Hz, 3H) ppm.

(268) .sup.13C NMR (CD.sub.2Cl.sub.2, 125 MHz): δ=296.2, 296.0, 268.5, 152.8, 146.6, 145.4, 143.8, 134.6, 132.1, 131.7, 131.0, 130.1, 127.6, 126.6, 124.4, 124.1, 123.6, 122.3, 113.4, 79.0, 75.5, 56.7, 52.7, 34.8, 31.0, 30.2, 29.6, 29.4, 29.2, 25.4, 24.4, 23.8, 23.4, 22.4, 22.3 ppm.

(269) HRMS-ESI calculated for C.sub.34H.sub.45NOKCl.sub.2Ru [M+K].sup.+: 694.1559; found 694.1552.

(270) Elemental analysis: calculated for C.sub.34H.sub.45NOCl.sub.2Ru:

(271) C, 62.28; H, 6.92; N, 2.14; Cl, 10.81; found: C, 62.25; H, 6.88; N, 1.98; Cl, 10.76.

Example XXXVI

(272) Application of Precatalysts 5a-5i in Ring-Closing Metathesis (RCM) Reactions of Diethyl Diallylomalonate S1 Leading to a Cyclic Compound P1.

(273) ##STR00066##

(274) To the solution of diethyl diallylomalonate S1 (480.6 mg, 2.0 mmol) in dry deoxygenated toluene (20 mL) at 40° C. or 60° C. a solution of respective precatalyst 5a-5i (0.002 mmol, 0.1 mol %) in dry deoxygenated toluene (50 μL) was added. The whole was stirred in argon atmosphere. At certain time intervals 0.1 mL samples of reaction mixture were collected to which one drop of ethyl vinyl ether was added to deactivate the catalyst. Conversion of substrate was determined by gas chromatography. A summary is presented in Table 4 (40° C.) and Table 5 (60° C.).

(275) TABLE-US-00004 TABLE 4 DEDAM conversion as a function of time for a reaction conducted at 40° C. T = 40° C. Time Conversion (%) (min) 5a 5c 5d 5h 5e 5g 5f 5i 1d 2 — 14 3 — 2 — — 6 4 — 25 6 — 7 — — 22 6 — 37 9 — 14 —  8 42 8 — 49 12 — 21 — — 60 10 — 60 15 0.2 30 0.7 3 13 73 15 — 81 24 — 48 — — 90 20 — 92 32 — 63 — 27 95 30 0.6 99 49 — 86 4 9 41 98 60 1   99.6 86 0.6 99 8 19 68 99.2 120 1.8 — 99 1.2 — 12 37 90 — 180 3 — — — — 18 52 96 —

(276) TABLE-US-00005 TABLE 5 DEDAM conversion as a function of time for reaction conducted at 60° C. T = 60° C. Time Conversion (%) (min) 5h 5g 5f 5i 2 — — 10 36 4 — — 21 69 6 —  4 33 85 8 — — 44 93 10  1  5 54 97 15 — — 74 99 20  3 — 86 99.6 30  6  7 96 99.7 60 22 10 99.6 99.8 120 63 20 — 180 89 38 —

Example XXXVII

(277) Application of Precatalysts 5c-5i in Ethenolysis Reactions of Methyl Oleate (MO).

(278) ##STR00067##

(279) To degassed MO (35.0 g, 118 mmol) a catalyst (10 ppm or 5 ppm) solution in dry deoxygenated toluene (100 μL) was added. The mixture was vacuum-pumped to an autoclave and stirred for 5 hours in a suitable temperature at 10 bar of ethylene. After 5 hours the reaction was quenched and after removal of ethylene from the reactor to the reaction mixture 0.1 mL 0.1 M SnatchCat solution [CAS: 51641-96-4] in methylene chloride was added to deactivate the catalyst. The samples were diluted with methylene chloride and analysed by gas chromatography. The conversions were calculated using residual methyl stearate as an internal standard. The results were summarised in Table 6.

(280) In order to determine the FID detector response factors to individual components of the reaction mixture a mixture of substrate-methyl oleate (MO), desired reaction products: 1-DECENE and 9-DAME, and reaction by-products OD-9-ENE and DIESTER-C18 diester according to the table below was prepared. The resulting mixture was diluted with toluene to 10 mL and analysed by gas chromatography. The area under the peak (AUP) for each component (mean of seven injections) was divided by the component mass of the analytical sample taking into account its purity and obtaining absolute response factor of a given component Rf′. Assuming the response factor of methyl oleate (MO) equal to Rf=1, from the proportions the absolute response factors Rf for remaining components were calculated.

(281) TABLE-US-00006 TABLE 6 Absolute Purity response factor Analytical according Area under Rf′ = AUP/ Response sample mass to GC the peak AUP (m × purity) factor Component [mg] [%] [μV × s] [μV × s/mg] for MO Rf 1-DECENE 23.91 99.9 101514.2 4249.9 0.63 9-DAME 28.74 98.0 112831.5 4006.1 0.60 OD-9-ENE 20.65 98.0 145112.4 7170.6 1.07 MO 18.74 96.3 121077.7 6709.2 1.00 DIESTER-C18 19.75 97.4 102791.4 5343.6 0.80

(282) In the further calculations, the area under the peak of a given component on the chromatogram was converted into percentage in the mixture using response factors calculated above.

(283) Reaction selectivity (S) was determined from the formula:
S=100×(n.sub.1-DECENE+n.sub.9-DAME)/[(n.sub.1-DECENE+n.sub.9-DAME)+2×(n.sub.OD-9-ENE+n.sub.DIESTER-C18)],
where n is the number of moles

(284) Reaction yield (Y) was determined from the formula:
Y=Conversion×Selectivity/100
TON=Reaction yield/catalyst amount in ppm×10000.

(285) TABLE-US-00007 TABLE 7 Methyl oleate (MO) ethenolysis with 5c-5i and 1d precatalysts application. Pre- 9-DAME catalyst Conver- content Selec- Pre- amount T sion in the tivity Yield catalyst (ppm) (° C.) (%) mixture (%) (%) TON 5c 10 50 59 34 89 53 52782 5c 5 50 41 28 91 37 73855 5d 10 60 53 31 89 47 46876 5e 10 50 70 40 88 61 61361 5e 5 60 48 31 90 43 86025 5f 10 60 21 16 92 19 18930 5i 10 65 55 34 87 48 47638 1d 10 40 61 34 91 56 56091 1d 5 40 51 33 92 46 92505

Example XXXVIII

(286) Application of Precatalyst 5c in Ring-Closing Metathesis (RCM) Reaction of Diallyl Tosylamide S2 Leading to a Cyclic Compound P2.

(287) ##STR00068##

(288) To solution of diallyl tosylamide S2 (205.0 mg, 0.816 mmol) in dry deoxygenated toluene (3 mL) at 55° C. a solution of precatalyst 5c (0.041 mg, 0.041 μmol, 50 ppm) in dry deoxygenated toluene (50 μL) was added. The whole was stirred in argon atmosphere. After 20 minutes a 0.1 mL sample of reaction mixture was collected to which a drop of 0.1 M SnatchCat solution was added to deactivate the catalyst. Conversion of substrate determined by gas chromatography was above 99.5%.

Example XXXIX

(289) Application of Precatalyst 5c in Ring-Closing Metathesis (RCM) Reaction of Compound S3 Leading to a Cyclic Compound P3.

(290) ##STR00069##

(291) To solution of compound S3 (212.0 mg, 0.776 mmol) in dry deoxygenated toluene (3 mL) at 55° C. solution of precatalyst 5c (0.039 mg, 0.039 μmol, 50 ppm) in dry deoxygenated toluene (50 μL) was added. The whole was stirred in argon atmosphere. After 1 hour a 0.1 mL sample of reaction mixture was collected to which a drop of 0.1 M SnatchCat solution was added to deactivate the catalyst. Conversion of substrate determined by gas chromatography was above 99.5%. No by-products were observed.

(292) .sup.1H NMR (CDCl.sub.3, 500 MHz): δ=7.39-7.27 (m, 5H), 5.74-5.62 (m, 2H), 5.19-5.10 (m, 2H), 4.46-4.06 (m, 2H), 3.64-3.56 (m, 1H), 2.26-2.08 (m, 2H), 1.93-1.67 (m, 2H), 1.15 (dd, J=6.4; 4.5 Hz, 3H) ppm.

(293) .sup.13C NMR (CDCl.sub.3, 125 MHz): δ=156.04, 155.96, 137.2, 137.1, 131.7, 131.4, 128.4, 128.3, 127.8, 127.7, 127.6, 127.4, 66.9, 66.7, 52.5, 52.3, 39.4, 39.1, 34.0, 33.9, 27.1, 26.9, 19.6, 19.1 ppm.

Example XXXX

(294) Application of Precatalyst 5c in Homometathesis Reaction of 9-Decenoic Acid Methyl Ester 9-DAME Leading to Compound DIESTER-C18.

(295) ##STR00070##

(296) To 9-decenoic acid methyl ester 9-DAME (5.53 g, 30.0 mmol) at 60° C. a solution of precatalyst 5c (0.060 mg, 0.060 μmol, 2 ppm) in dry deoxygenated toluene (50 μL) was added. The whole was stirred in argon atmosphere (argon was bubbled through the reaction mixture). After 2 hours the reaction mixture was cooled to the ambient temperature, 5 drops of 0.1 M SnatchCat solution were added and reaction mixture was stirred for the next 30 minutes.

(297) In order to plot standard curves two analytical samples of substrate and product, respectively, were prepared. Analytical samples were diluted to obtain respective standard solution concentrations. Graphs depicting relationship between area under the peak (AUP) on the chromatogram and the concentration (mg/mL) of the analysed compound were shown in the FIG. 2.

(298) 28.70 mg of the analytical sample of the post-reaction mixture was prepared and diluted to 10 mL (2.87 mg/mL).

(299) On the chromatogram of such obtained solution AUP for the substrate was 166469.8 μV×s (mean of three injections) and AUP for product was 47666.1 μV×s (mean of three injections), what corresponded to the substrate concentration of 0.89 mg/mL (based on the substrate standard curve) and product concentration of 1.95 mg/mL (based on the product standard curve).

(300) Conversion and yield were determined from the formulas:
Conversion=100%×(1−(0.89/2.87))=68.99%
Yield=100%×1.95/2.87=67.94%.
Selectivity=100%×Yield/Conversion=98.48%.
TON=169850.

(301) A mixture of E/Z isomers (1.5:1).

(302) .sup.1H NMR (CDCl.sub.3, 500 MHz): δ=5.36 (ddd, J=5.3; 3.7; 1.6 Hz, 2H, E), 5.32 (ddd, J=5.7; 4.3; 1.1 Hz, 2H, Z), 3.65 (s, 6H), 2.29 (t, J=7.5 Hz, 4H), 2.03-1.90 (m, 4H), 1.68-1.56 (m, 4H), 1.35-1.23 (m, 16H) ppm.

(303) .sup.13C NMR (CDCl.sub.3, 125 MHz): δ=174.25 (E), 174.24 (Z), 130.3 (E), 129.8 (Z), 51.4, 34.1, 32.5, 29.6 (Z), 29.5 (E), 29.12 (Z), 29.08 (E), 29.07 (E), 29.05 (Z), 28.9, 27.1 (Z), 24.9 (E) ppm.

Example XXXXI

(304) Application of Precatalyst 5c in Homometathesis Reaction of 1-DECENE Leading to Octadec-9-Ene E.

(305) ##STR00071##

(306) To 1-DECENE (5.22 g, 37.2 mmol) at 60° C. a solution of precatalyst 5c (0.037 mg, 0.037 μmol, 1 ppm) in dry deoxygenated toluene (50 μL) was added. The whole was stirred in argon atmosphere (argon was bubbled through the reaction mixture). After 2 hours the reaction mixture was cooled to the ambient temperature, 5 drops of 0.1 M SnatchCat solution were added and it was stirred for the next 30 minutes. Then two solutions of reaction mixture with known concentration were prepared separately. Conversion (64%) and yield (63%) were determined by gas chromatography using external standard method (calculations are performed analogously to those shown in Example XXXX). Graphs depicting relationship between area under the peak (AUP) on the chromatogram and the concentration (mg/mL) of the analysed compound were shown in the FIG. 3. Reaction selectivity 98%. TON was 316398.

(307) A mixture of E/Z isomers (4:1).

(308) .sup.1H NMR (CDCl.sub.3, 500 MHz): δ=5.39 (ddd, J=5.3; 3.7; 1.6 Hz, 2H, E), 5.35 (ddd, J=5.7; 4.4; 1.1 Hz, 2H, Z), 2.06-1.91 (m, 4H), 1.38-1.18 (m, 24H), 0, 88 (t, J=6.9 Hz, 6H) ppm.

(309) .sup.13C NMR (CDCl.sub.3, 125 MHz): δ=130.4 (E), 129.9 (Z), 32.6, 31.9, 29.8 (Z), 29.7 (E), 29.53 (Z), 29.51 (E), 29.3, 29.2 (E), 27.2 (Z), 22.7, 14.1 ppm.

Example XXXXII

(310) Application of Precatalyst 5c in Cross-Metathesis Reaction of 9-Decenoic Acid Methyl Ester 9-DAME with Acrylonitrile S6 Leading to Compound P6.

(311) ##STR00072##

(312) To solution of 9-decenoic acid methyl ester 9-DAME (184.0 mg, 1.0 mmol) in dry deoxygenated toluene (20 mL) acrylonitrile S6 (99 μL, 1.50 mmol, 1.5 molar equivalents) and methyl stearate (10 mg, internal standard) were added at 60° C., following by a solution of precatalyst 5c (0.1 mg, 0.1 μmol, 100 ppm) in dry deoxygenated toluene (50 μL). Reaction mixture was stirred in argon atmosphere. After 1 hour and then after 2 hours further portions of precatalyst 5c (2×0.05 mg, 0.05 μmol, 50 ppm) in dry deoxygenated toluene (50 μL) were added. Totally 0.2 mg, 0.2 μmol, 200 ppm precatalyst 5c was used. After another hour 0.1 mL reaction mixture sample was collected to which a drop of 0.1 M SnatchCat solution was added to deactivate the catalyst. Conversion of substrate determined by gas chromatography with internal standard was 87%. Content of the P6 product on the chromatogram was 75%.

(313) A mixture of E/Z isomers (1:4).

(314) .sup.1H NMR (CDCl.sub.3, 500 MHz): δ=6.69 (dt, J=16.4; 7.0 Hz, 1H, E), 6.46 (dt, J=10.9; 7.7 Hz, 1H, Z), 5.30 (dt, J=16.4; 1.7 Hz, 1H, E), 5.29 (dt, J=10.9; 1.3 Hz, 1H, Z), 3.65 (s, 3H, E+3H, Z), 2.40 (dq, J=7.6; 1.3 Hz, 2H, Z), 2.29 (t, J=7.5 Hz, 2H, E+2H, Z), 2.20 (qd, J=7.1; 1.7 Hz 2H, E), 1.64-1.54 (m, 2H, E+2H, Z), 1.50-1.39 (m, 2H, E+2H, Z), 1.36-1.26 (m, 6H, E+6H, Z) ppm.

(315) .sup.13C NMR (CDCl.sub.3, 125 MHz): δ=174.12 (Z), 174.08 (E), 156.0 (E), 155.0 (Z), 117.5 (E), 116.0 (Z), 99.6 (E), 99.5 (Z), 51.39 (E), 51.37 (Z), 33.95 (Z), 33.92 (E), 33.2 (E) 31.7 (Z), 28.87 (Z), 28.85 (E), 28.83 (Z+E), 28.72 (Z), 28.68 (E), 28.1 (Z), 27.5 (E), 24.77 (Z), 24.75 (E) ppm.

Example XXXXIII

(316) Application of Precatalyst 5c in Cross-Metathesis Reaction of 9-Decenoic Acid Methyl Ester 9-DAME with Methyl Acrylate S7 Leading to Compound P7.

(317) ##STR00073##

(318) To solution of 9-decenoic acid methyl ester 9-DAME (400.0 mg, 2.17 mmol) in dry deoxygenated toluene (4 mL) methyl acrylate S7 (0.98 mL, 10.9 mmol, 5 molar equivalents), methyl stearate (20 mg, internal standard) were added at 60° C., following by a solution of precatalyst 5c (0.109 mg, 0.109 μmol, 50 ppm) in dry deoxygenated toluene (50 μL). The whole was stirred in argon atmosphere. After 1 hour, 2 hours and 3 hours further portions of precatalyst 5c (3×0.109 mg, 0.109 μmol, 50 ppm) in dry deoxygenated toluene (50 μL) were added. Totally 0.436 mg, 0.436 μmol, 200 ppm of precatalyst 5c was used. After another hour 0.1 mL reaction mixture sample was collected to which a drop of 0.1 M SnatchCat solution was added to deactivate the catalyst. Conversion of substrate determined by gas chromatography with an internal standard was 99%. Content of product P7 in postreaction mixture was 97%.

(319) A mixture of E/Z isomers (87:13).

(320) Isomer E:

(321) .sup.1H NMR (CDCl.sub.3, 500 MHz): δ=6.94 (dt, J=15.7; 7.0 Hz, 1H), 5.80 (dt, J=15.6; 1.6 Hz, 1H), 3.71 (s, 3H), 3.65 (s, 3H), 2.28 (t, J=7.5 Hz, 2H), 2.17 (dq, J=7.1; 1.6 Hz, 2H), 1.64-1.56 (m, 2H), 1.47-1.39 (m, 2H), 1.33-1.26 (m, 6H) ppm.

(322) .sup.13C NMR (CDCl.sub.3, 125 MHz): δ=174.2, 167.1, 149.6, 133.4, 120.8, 51.4, 51.3, 34.0, 32.1, 29.0, 28.9, 27.9, 24.8 ppm.

(323) Isomer Z:

(324) .sup.1H NMR (CDCl.sub.3, 500 MHz): δ=6.22 (dt, J=11.6; 7.5 Hz, 1H), 5.76 (dt, J=11.5; 1.7 Hz, 1H), 3.70 (s, 3H), 3.66 (s, 3H), 2.64 (dq, J=7.5; 1.7 Hz, 2H), 2.30 (t, J=7.5 Hz, 2H), 1.65-1.56 (m, 2H), 1.47-1.39 (m, 2H), 1.34-1.28 (m, 6H) ppm.

(325) .sup.13C NMR (CDCl.sub.3, 125 MHz): δ=174.3, 166.8, 150.8, 119.2, 51.4, 51.0, 34.1, 29.1, 29.0, 28.9, 24.9, 24.8 ppm.

Example XXXXIV

(326) Application of Precatalyst 5c in Ring-Closing Metathesis Reaction of S8 Leading to Compound P8 Having a Tetrasubstituted Double Bond.

(327) ##STR00074##

(328) To solution of compound S8 (509.0 mg, 1.82 mmol) in dry deoxygenated toluene (6.8 mL) at 60° C., in argon atmosphere every 10 minutes a solution of precatalyst 5c (0.182 mg, 0.182 μmol, 100 ppm) in dry deoxygenated toluene (50 μL) was added up to a total amount of 1000 ppm of precatalyst 5c (10 portions). The whole was stirred in argon atmosphere for an additional hour. 0.1 mL of the reaction mixture sample was collected to which a drop of 0.1 M SnatchCat solution was added to deactivate the catalyst. Conversion of substrate determined by gas chromatography was 90%. The product was isolated by column chromatography on silica gel. White solid, 361 mg (79%).

(329) .sup.1H NMR (CDCl.sub.3, 500 MHz): δ=7.70 (d, J=8.2 Hz, 2H), 7.30 (d, J=8.0 Hz, 2H), 3.96 (s, 4H), 2.41 (s, 3H), 1.53 (s, 6H) ppm.

(330) .sup.13C NMR (CDCl.sub.3, 125 MHz): δ=143.2, 134.2, 129.6, 127.4, 126.1, 58.7, 21.4, 11.0 ppm.

Example XXXXV

(331) Application of Precatalyst 5c in Homometathesis Reaction of Methyl Oleate MO Leading to OD-9-ENE and DIESTER-C18 Compounds.

(332) ##STR00075##

(333) To methyl oleate MO (19.52 g, 65.9 mmol) at 60° C. in argon atmosphere every 30 minutes a solution of precatalyst 5c (0.066 mg, 0.066 μmol, 1 ppm) in dry deoxygenated toluene (50 μL) was added, up to 5 ppm of precatalyst 5c (5 portions). The whole was stirred in argon atmosphere for an additional hour. A drop of reaction mixture was collected and diluted with ethyl acetate to 1 mL, and then a drop of 0.1 M SnatchCat solution was added to deactivate the catalyst. The sample was analysed by gas chromatography. In the chromatogram obtained the OD-9-ENE/MO/DIESTER-C18 area ratio was 21%/57%/22%, respectively.

Example XXXXVI

(334) Application of Precatalyst 5c in Ring-Closing Metathesis Reaction of Compound S9 Leading to Macrocyclic Lactone P9.

(335) ##STR00076##

(336) To solution of compound S9 (213.0 mg, 0.799 mmol) in dry deoxygenated toluene (160 mL, C.sub.S9=5 mM) at 70° C., in argon atmosphere every 15 minutes a solution of precatalyst 5c (0.040 mg, 0.040 μmol, 50 ppm) in dry deoxygenated toluene (50 μL) was added up to a total amount of (pre)catalyst 250 ppm (5 portions). The whole was stirred in argon atmosphere for an additional hour. 1 mL of the reaction mixture sample was collected to which a drop of 0.1 M SnatchCat solution was added to deactivate the catalyst. Conversion of substrate determined by gas chromatography with external standard was 95%. E/Z=65:35. Standard curve for product P9 was shown in the FIG. 4.

(337) Postreaction mixture was analysed with GC without further dilutions. Cumulative area under the peaks (E and Z isomers) of the product was 1165868 (mean of three injections). Product concentration in postreaction mixture was 4.56 mM (C=1165868/255756). Yield GC Y=4.56 mM×100%/5 mM=91%.

(338) .sup.1H NMR (CDCl.sub.3, 500 MHz): δ=5.43-5.23 (m, 2H), 4.13 (t, J=6.3 Hz, 2H, Z), 4.11 (t, J=7.1 Hz, 2H, E), 2.35-2.27 (m, 2H), 2.07-1.98 (m, 4H), 1.67-1.55 (m, 4H), 1.44-1.16 (m, 12H) ppm.

(339) .sup.13C NMR (CDCl.sub.3, 125 MHz): δ=173.8, 131.8 (E), 130.3 (E), 130.1 (Z), 129.5 (Z), 64.1 (Z), 63.9 (E), 34.7 (E), 33.8 (Z), 32.0 (E), 31.9 (E), 29.1 (Z), 28.4 (Z), 28.3 (E), 28.3 (E), 28.2 (E), 28.1 (Z), 28.0 (E), 27.9 (Z), 27.6 (Z), 27.21 (E), 27.18 (Z), 27.1 (Z), 26.6 (Z), 26.5 (E), 26.4 (Z), 25.4 (E), 25.20 (Z), 25.18 (E) ppm.

Example XXXXVII

(340) Preparation Method of Precatalyst 1d without CuCl.

(341) ##STR00077##

(342) To salt 3ab (0.345 g, 1.0 mmol, 2 molar equivalents) dry deoxygenated toluene (4 mL) was added in argon atmosphere. The mixture was heated to 80° C. and solution of LiHMDS in toluene (1 M, 1.0 mL, 1.0 mmol, 2 molar equivalents) was added. After 1 minute solid complex M10 (0.443 g, 0.5 mmol, 1 molar equivalent) was added. After 2 minutes benzylidene ligand 4a (0.176 g, 1.0 mmol, 2.0 molar equivalents) was added. The whole was stirred for 30 minutes at 105° C. and cooled down to the room temperature. The crude product was isolated by column chromatography on silica gel (eluent: toluene). Green fraction was collected and concentrated to dryness. The residue was dissolved in ethyl acetate and evaporated and the residue was washed with isopropanol and dried under high vacuum giving green crystalline solid-precatalyst 1d (0.130 g, 45%).

(343) Analytical data for product 1d obtained by this method were identical as in Example VII.

Example XXXXVIII

(344) Preparation Method of Precatalyst 1m without CuCl.

(345) ##STR00078##

(346) To salt 3ad (0,407 g, 1.0 mmol, 2 molar equivalents) dry deoxygenated toluene (4 mL) was added in argon atmosphere. The mixture was heated to 80° C. and solution of LiHMDS in toluene (1 M, 1.0 mL, 1.0 mmol, 2 molar equivalents) was added. After 1 minute solid complex M10 (0.443 g, 0.5 mmol, 1 molar equivalent) was added. After 2 minutes benzylidene ligand 4a (0.176 g, 1.0 mmol, 2.0 molar equivalents) was added. The whole was stirred for 30 minutes at 105° C. and cooled down to the room temperature. The crude product was isolated by column chromatography on silica gel (eluent: toluene). Green fraction was collected and concentrated to dryness. The residue was dissolved in methylene chloride and excess of isopropanol was added. Methylene chloride was evaporated under reduced pressure, the resulting precipitate was filtrated off and washed with a small amount of isopropanol. It was dried under high vacuum giving green crystalline solid-precatalyst 1m (0.151 g, 47%). A mixture of A:B isomers=1:4.

(347) Due to a very complex .sup.1H NMR spectrum only the characteristic benzylidene proton shifts were given: isomer A: singlet 17.88 ppm, isomer B: singlet 16.51 ppm (C.sub.6D.sub.6).

Example XXXXIX

(348) Preparation Method of Intermediate 5a from First Generation Precursor M10

(349) ##STR00079##

(350) To salt 3aa (10.00 g, 29.0 mmol, 3 molar equivalents) dry deoxygenated toluene (50 mL) was added in argon atmosphere. The mixture was heated to 80° C. and solution of LiHMDS in toluene (1 M, 29.0 mL, 29.0 mmol, 3 molar equivalents) was added. After 1 minute solid complex M10 (8.56 g, 9.66 mmol, 1 molar equivalent) was added. After 5 minutes the mixture was cooled down to the room temperature. Reaction mixture was filtrated through a small amount of silica gel and washed with toluene. The crude product was isolated by column chromatography on silica gel (eluent: ethyl acetate/cyclohexane 1:9 v/v). Red fraction was collected and concentrated to dryness. It was dissolved in n-pentane and slowly concentrated to dryness (the product crystallised during solvent removal). Red crystalline solid was obtained—an intermediate compound 5a (5.02 g, 59%). Comparison with Example XV.

(351) The project leading to this application has received funding from the European Union's Horizon 2020 research and innovation programme under grant agreement No 635405.