Ruthenium complexes useful for catalyzing metathesis reactions

Abstract

Compound of formula 4 or formula 5 ##STR00001##
wherein
L is a neutral ligand, preferably a nitrogen-containing heterocyclic carbene (NHC) such as carbene containing at least two nitrogen atoms, a cyclic aminoalkyl carbene (CAAC) or a bicyclic aminoalkyl carbene (BICAAC);
R.sup.1, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10 and R.sup.11 are, independently, H, unbranched or branched C.sub.1-20 alkyl, C.sub.5-9 cycloalkyl, unbranched or branched C.sub.1-20 alkoxy, optionally bearing one or more halogen atoms, respectively; or aryl, optionally substituted with one or more of unbranched or branched C.sub.1-20 alkyl, C.sub.5-9 cycloalkyl, unbranched or branched C.sub.1-20 alkoxy, aryl, aryloxy, unbranched or branched C.sub.1-20 alkylcarbonyl, arylcarbonyl, unbranched or branched C.sub.1-20 alkoxycarbonyl, aryloxycarbonyl, heteroaryl, carboxyl, cyano, nitro, amido, aminosulfonyl, N-heteroarylsulfonyl, unbranched or branched C.sub.1-20 alkylsulfonyl, arylsulfonyl, unbranched or branched C.sub.1-20 alkylsulfinyl, arylsulfinyl, unbranched or branched C.sub.1-20 alkylthio, arylthio, sulfonamide, halogen or N(R.sup.y)(R.sup.z), wherein R.sup.y and R.sup.z are independently selected from H and C.sub.1-20 alkyl:
R.sup.2 is H, unbranched or branched C.sub.1-20 alkyl.

Claims

1. A ruthenium complex having the structure of formula I-c: ##STR00103## wherein: each of R.sup.6 and R.sup.7 is independently R, —CN, halogen, —OR, —OC(O)R, —OSiR.sub.3, —SR, —S(O)R, —S(O).sub.2R, —NO.sub.2, —N(R′).sub.2, —NR′C(O)R, —NR′C(O)OR, —NR′C(O)N(R′).sub.2, —NR′SO.sub.2R, —NR′SO.sub.2N(R′).sub.2, —NR′OR, —SeR, —SiR.sub.3; or R.sup.6 and R.sup.7 are optionally taken together with their intervening atoms to form an optionally substituted 3-10 membered, saturated, partially unsaturated or aryl monocyclic or bicyclic ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or wherein the complex has the structure of formula I-d: ##STR00104## or wherein the complex has the structure of formula I-e: ##STR00105## or wherein the complex has the structure of formula I-f: ##STR00106## wherein in each of formulas I-c to I-f: R.sup.1 is a carbene of formula 7a ##STR00107## wherein each R in formula 7a is independently hydrogen, C.sub.1-C.sub.12 alkyl, C.sub.3-C.sub.12 cycloalkyl, C.sub.2-C.sub.12 alkenyl, C.sub.6-C.sub.14 aryl, C.sub.1-C.sub.5 perfluoroalkyl, C.sub.7-C.sub.24 aralkyl, or C.sub.6-C.sub.14 perfluoroaryl group, which are optionally substituted with at least one C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perfluoroalkyl, C.sub.1-C.sub.12 alkoxy, C.sub.6-C.sub.14 aryloxy, or a halogen atom; and wherein two R which are separated by the C—CR.sub.2—C moiety can be combined with to form a cyclic system; or is a carbene of formula 7b ##STR00108## wherein each R in formula 7b is independently hydrogen, C.sub.1-C.sub.12 alkyl, C.sub.3-C.sub.12 cycloalkyl, C.sub.2-C.sub.12 alkenyl, C.sub.6-C.sub.14 aryl, C.sub.1-C.sub.5 perfluoroalkyl, C.sub.7-C.sub.24 aralkyl, or C.sub.6-C.sub.14 perfluoroaryl group, which are optionally substituted with at least one C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perfluoroalkyl, C.sub.1-C.sub.12 alkoxy, C.sub.6-C.sub.14 aryloxy, or a halogen atom; and wherein n is 1, 2 or 3; or is a carbene of formula 7c ##STR00109## wherein in formula 7c m is an integer of from 0 to 4, and each R.sup.y independently has the meaning of C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perfluoroalkyl, C.sub.1-C.sub.12 alkoxy, C.sub.6-C.sub.14 aryl, C.sub.6-C.sub.14 aryloxy, or halogen; or is a carbene of formula 7d ##STR00110## wherein in formula 7d m is an integer of from 0 to 4, and each R.sup.y independently has the meaning of C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perfluoroalkyl, C.sub.1-C.sub.12 alkoxy, C.sub.6-C.sub.14 aryl, C.sub.6-C.sub.14 aryloxy, or halogen; or is a carbene of formula 7e ##STR00111## or is a carbene of formula 7f ##STR00112## or is a carbene of formula 7g or 7h ##STR00113## or is a carbene of formula 7i ##STR00114## or is a carbene of formula 7k ##STR00115## wherein each R in formulae 7c to 7i is independently hydrogen or C.sub.1-C.sub.12 alkyl, or C.sub.3-C.sub.12 cycloalkyl, or C.sub.2-C.sub.12 alkenyl, C.sub.6-C.sub.14 aryl, C.sub.1-C.sub.5 perfluoroalkyl, C.sub.7-C.sub.24 aralkyl, or C.sub.6-C.sub.14 perfluoroaryl group, which are optionally substituted with at least one C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perfluoroalkyl, C.sub.1-C.sub.12 alkoxy, C.sub.6-C.sub.14 aryloxy, or a halogen atom; wherein Ar as defined in formulae 7a to 7k is aryl, optionally substituted with one or more groups selected from: C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perfluoroalkyl, C.sub.1-C.sub.12 alkoxy, C.sub.6-C.sub.14 aryloxy, or halogen; r is 1; X and Y are —S—; Ring A is an optionally substituted ring selected from phenyl, an 8-10 membered bicyclic aryl ring, a 5-6 membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or an 8-10 membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; each R.sup.x is independently halogen, R, —CN, —C(O)N(R′).sub.2, —C(O)R, —C(O)OR, —OR, —OC(O)R, —OC(O)OR, —OC(O)N(R′).sub.2, —OSiR.sub.3, —N(R′).sub.2, —N(R′).sub.3.sup.+, —NR′C(O)R, —NR′C(O)OR, —NR′C(O)N(R′).sub.2, —NR′SO.sub.2R, —NR′SO.sub.2N(R′).sub.2, —NR′OR, —NO.sub.2, —SiR.sub.3, —PR.sub.2, —P(O)R.sub.2, —P(O)(OR).sub.2, —SR, —SC(O)R, —S(O)R, —SO.sub.2R, —SO.sub.3R, —SO.sub.2N(R′).sub.2, or —SeR, each R′ is independently R, —C(O)R, —C(O)NR.sub.2, —C(O)OR, —SO.sub.2R, —SO.sub.2NR.sub.2, —P(O)(OR).sub.2, or —OR; each R is independently hydrogen or an optionally substituted group selected from C.sub.1-20 aliphatic, C.sub.1-20 heteroaliphatic, phenyl, a 3-7 membered saturated or partially unsaturated carbocyclic ring, an 8-10 membered bicyclic saturated, partially unsaturated or aryl ring, a 5-6 membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 3-7 membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 7-10 membered bicyclic saturated or partially unsaturated heterocyclic ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or an 8-10 membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or: two R groups are optionally taken together with their intervening atoms to form an optionally substituted 3-10 membered, saturated, partially unsaturated, or aryl ring having, in addition to the intervening atoms, 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; m is 0-6; R.sup.2 is H; R.sup.3 is hydrogen or an optionally substituted group selected from C.sub.1-20 aliphatic, C.sub.1-20 heteroaliphatic, phenyl, a 3-7 membered saturated or partially unsaturated carbocyclic ring, a 5-6 membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or a 3-7 membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and Z is —O—.

2. The complex of claim 1, wherein the complex has the structure of formula I-g: ##STR00116##

3. The complex of claim 1, wherein the carbene of formula 7a is of formula 7a′ ##STR00117## wherein R.sup.12, R.sup.13, R.sup.14, and R.sup.15 in formula 7a are each independently hydrogen, C.sub.1-C.sub.12 alkyl, C.sub.3-C.sub.12 cycloalkyl, C.sub.2-C.sub.12 alkenyl, C.sub.6-C.sub.14 aryl, C.sub.1-C.sub.5 perfluoroalkyl, C.sub.7-C.sub.24 aralkyl, or C.sub.6-C.sub.14 perfluoroaryl group, which are optionally substituted with at least one C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perfluoroalkyl, C.sub.1-C.sub.12 alkoxy, C.sub.6-C.sub.14 aryloxy, or a halogen atom; and wherein R.sup.12 and/or R.sup.13 can be combined with R.sup.14 and/or R.sup.15 to form a cyclic system; or wherein the carbene of formula 7b is of formula 7b′: ##STR00118## wherein R.sup.16, R.sup.17 and R.sup.18 in formula 7b′ are each independently hydrogen or C.sub.1-C.sub.12 alkyl, or C.sub.3-C.sub.12 cycloalkyl, or C.sub.2-C.sub.12 alkenyl, C.sub.6-C.sub.14 aryl, C.sub.1-C.sub.5 perfluoroalkyl, C.sub.7-C.sub.24 aralkyl, or C.sub.6-C.sub.14 perfluoroaryl group, which are optionally substituted with at least one C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perfluoroalkyl, C.sub.1-C.sub.12 alkoxy, C.sub.6-C.sub.14 aryloxy, or a halogen atom.

4. The complex of claim 1, wherein the complex is ##STR00119##

5. The complex of claim 1, wherein the complex is immobilized on a solid support.

6. A method of catalysing a metathesis reaction, comprising: metathesizing one or more olefins in the presence of a complex as defined in claim 1.

7. The method of claim 6, wherein more than 80% of the olefins formed in the catalysed metathesis reaction are Z-olefins.

8. The complex of claim 1, wherein Ar as defined in formulae 7a to 7k is phenyl, optionally substituted with one or more groups selected from: C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perfluoroalkyl, C.sub.1-C.sub.12 alkoxy, C.sub.6-C.sub.14 aryloxy, or halogen.

9. The complex of claim 1, wherein R in formula 7b are each independently hydrogen, C.sub.1-C.sub.12 alkyl, or C.sub.3-C.sub.12 cycloalkyl.

10. The complex of claim 3, wherein R.sup.16, R.sup.17 and R.sup.18 in formula 7b′ are each independently hydrogen, C.sub.1-C.sub.12 alkyl, or C.sub.3-C.sub.12 cycloalkyl.

11. The complex of claim 1, wherein each R in formulae 7c to 7i is hydrogen, C.sub.1-C.sub.12 alkyl, or C.sub.3-C.sub.12 cycloalkyl.

12. The complex of claim 1, wherein the carbene of formula 7c is a carbene of formula 7c′ ##STR00120##

13. The complex of claim 1, wherein the carbene of formula 7d is a carbene of formula 7d′ ##STR00121##

14. The complex of claim 1, wherein each R in formula 7b is independently hydrogen, C.sub.1-C.sub.12 alkyl, or C.sub.3-C.sub.12 cycloalkyl, optionally substituted with at least one C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perfluoroalkyl, C.sub.1-C.sub.12 alkoxy, C.sub.6-C.sub.14 aryloxy, or a halogen atom.

15. The complex of claim 1, wherein Ar as defined in formulae 7a to 7k is phenyl, optionally substituted with one or more groups selected from: C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perfluoroalkyl, C.sub.1-C.sub.12 alkoxy, C.sub.6-C.sub.14 aryloxy, or halogen.

Description

DETAILED DESCRIPTION OF THE INVENTION

(1) All terms in quotation marks are defined in the meaning of the invention.

(2) In a first aspect, the invention relates to a compound of formula 4 or formula 5:

(3) ##STR00053## wherein in formula 4 or formula 5 the substituents L and R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10 and R.sup.11 have the following meaning: L is: a neutral ligand; R.sup.1 is: H; unbranched or branched C.sub.1-20 alkyl or unbranched or branched C.sub.1-20 alkoxy; C.sub.5-9 cycloalkyl or C.sub.5-9 cycloalkoxy; optionally bearing one or more halogen atoms, respectively; or aryl or aryloxy; optionally substituted, respectively, with one or more of unbranched or branched C.sub.1-20 alkyl, C.sub.5-9 cycloalkyl, unbranched or branched C.sub.1-20 alkoxy, C.sub.5-9 cycloalkoxy, aryl, aryloxy, unbranched or branched C.sub.1-20 alkylcarbonyl, arylcarbonyl, unbranched or branched C.sub.1-20 alkoxycarbonyl, aryloxycarbonyl, heteroaryl, carboxyl, cyano, nitro, amido, aminosulfonyl, N-heteroarylsulfonyl, unbranched or branched C.sub.1-20 alkylsulfonyl, arylsulfonyl, unbranched or branched C.sub.1-20 alkylsulfinyl, arylsulfinyl, unbranched or branched C.sub.1-20 alkylthio, arylthio, sulfonamide, halogen or N(R.sup.y)(R.sup.z), wherein R.sup.y and R.sup.z are independently selected from H and C.sub.1-20 alkyl; R.sup.2 is: H; unbranched or branched C.sub.1-20 alkyl; aryl; —C(O)R.sup.12; —C(O)OR.sup.12, —C(O)C(O)R.sup.12; —C(O)C(O)OR.sup.12, wherein R.sup.12 has the meaning of C.sub.1-20 alkyl or aryl, respectively; R.sup.12 optionally bearing one or more halogen atoms; R.sup.3 is: unbranched or branched C.sub.1-20 alkyl; aryl; or R.sup.13—C(O)—CHR.sup.14, wherein R.sup.13 is C.sub.1-20 alkoxy and R.sup.14 is H or C.sub.1-20 alkyl; or wherein R.sup.13 is C.sub.1-20 alkoxy and R.sup.14 is C(O)—O—C.sub.1-20 alkyl; or wherein R.sup.13 is C.sub.1-20 alkyl and R.sup.14 is H; or R.sup.13 is OH and R.sup.14 is H or C.sub.1-20 alkyl; or R.sup.15—O—N(R.sup.16)—C(O)—CHR.sup.17, wherein R.sup.15, R.sup.16, and R.sup.17 are independently H or C.sub.1-20 alkyl; R.sup.4 is: H; R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10 and R.sup.11 are, independently, H; unbranched or branched C.sub.1-20 alkyl or unbranched or branched C.sub.1-20 alkoxy; C.sub.5-9 cycloalkyl or C.sub.5-9 cycloalkoxy; aryl; aryloxy; unbranched or branched C.sub.1-20 alkylcarbonyl; arylcarbonyl; unbranched or branched C.sub.1-20 alkoxycarbonyl; aryloxycarbonyl; heteroaryl; carboxyl; cyano; nitro; amido; aminosulfonyl; N-heteroarylsulfonyl; unbranched or branched C.sub.1-20 alkylsulfonyl; arylsulfonyl; unbranched or branched C.sub.1-20 alkylsulfinyl; arylsulfinyl; unbranched or branched C.sub.1-20 alkylthio; arylthio; sulfonamide; halogen; or N(R.sup.y)(R.sup.z), wherein R.sup.y and R.sup.z are independently selected from H and C.sub.1-20 alkyl; or aryl or aryloxy, respectively substituted with one or more of unbranched or branched C.sub.1-20 alkyl or unbranched or branched C.sub.1-20 alkoxy, C.sub.5-9 cycloalkyl or C.sub.5-9 cycloalkoxy, aryl, aryloxy, unbranched or branched C.sub.1-20 alkylcarbonyl, arylcarbonyl, unbranched or branched C.sub.1-20 alkoxycarbonyl, aryloxycarbonyl, heteroaryl, carboxyl, cyano, nitro, amido, aminosulfonyl, N-heteroarylsulfonyl, unbranched or branched C.sub.1-20 alkylsulfonyl, arylsulfonyl, unbranched or branched C.sub.1-20 alkylsulfinyl, arylsulfinyl, unbranched or branched C.sub.1-20 alkylthio, arylthio, sulfonamide, halogen or N(R.sup.y)(R.sup.z), wherein R.sup.y and R.sup.z are independently selected from H and C.sub.1-20 alkyl.

(4) In a preferred embodiment, the term “C.sub.1-20 unbranched or branched alkyl” means C.sub.1-6 alkyl.

(5) The term “unbranched or branched C.sub.1-20 alkyl, unbranched or branched C.sub.1-20 alkoxy, C.sub.5-9 cycloalkyl, C.sub.5-9 cycloalkoxy, optionally bearing one or more halogen atoms” encompasses in a preferred embodiment perhalogenated residues.

(6) Preferred perhalogenated residues are CCl.sub.3, CF.sub.3, C.sub.2F.sub.5, C.sub.3F.sub.7, C.sub.4F.sub.9, C.sub.5F.sub.11, C.sub.6F.sub.13, C.sub.7F.sub.15 and C.sub.8F.sub.17.

(7) In particular with respect to R.sup.1, the term “C.sub.1-20 unbranched or branched alkyl (optionally) bearing one or more halogen atoms” encompasses in a preferred embodiment perhalogenated residues. Preferred perhalogenated residues are CCl.sub.3, CF.sub.3, C.sub.2F.sub.5, C.sub.3F.sub.7, C.sub.4F.sub.9, C.sub.5F.sub.11, C.sub.6F.sub.13, C.sub.7F.sub.15 and C.sub.8F.sub.17.

(8) The term “aryl” encompasses C.sub.6, C.sub.10 and C.sub.14 aryl. A preferred aryl residue is phenyl or naphthyl.

(9) In one embodiment, each aryl residue may be optionally substituted with one or more of unbranched or branched C.sub.1-20 alkyl, C.sub.5-9 cycloalkyl, unbranched or branched C.sub.1-20 alkoxy, C.sub.5-9 cycloalkoxy, aryl, aryloxy, unbranched or branched C.sub.1-20 alkylcarbonyl, arylcarbonyl, unbranched or branched C.sub.1-20 alkoxycarbonyl, aryloxycarbonyl, heteroaryl, carboxyl, cyano, nitro, amido, aminosulfonyl, N-heteroarylsulfonyl, unbranched or branched C.sub.1-20 alkylsulfonyl, arylsulfonyl, unbranched or branched C.sub.1-20 alkylsulfinyl, arylsulfinyl, unbranched or branched C.sub.1-20 alkylthio, arylthio, sulfonamide, halogen, or N(R.sup.y)(R.sup.z), wherein R.sup.y and R.sub.z are independently selected from H and C.sub.1-20 alkyl.

(10) In one embodiment, the neutral ligand L is a phosphine.

(11) Preferably, the neutral ligand is of formula P(R.sup.x).sub.3, wherein R.sup.x is independently branched or unbranched C.sub.1-20 alkyl or C.sub.1-20 alkoxy, C.sub.5-9 cycloalkyl, or aryl. In a preferred embodiment, R.sup.x is cyclohexyl.

(12) In one embodiment, the neutral ligand is a nitrile.

(13) Preferably, the nitrile is of formula RCN, wherein R is branched or unbranched C.sub.1-20 alkyl, C.sub.5-9 cycloalkyl, or aryl.

(14) In a preferred embodiment, the neutral ligand L in formula 4 or 5 is a nitrogen-containing carbene, preferably an electron-donating nitrogen-containing carbene.

(15) In one embodiment, the carbene is a N-heterocyclic carbene (NHC).

(16) In one embodiment, the N-heterocyclic carbene (NHC) contains at least two nitrogen atoms.

(17) Preferably, the carbene contains the moiety of formula 6

(18) ##STR00054##
wherein R.sup.7 and R.sup.8 as defined in formula 6 are each independently H, unbranched or branched C.sub.1-20 alkyl, C.sub.5-9 cycloalkyl, or phenyl, wherein the phenyl is optionally substituted with up to three groups independently selected from unbranched or branched C.sub.1-6 alkyl, C.sub.1-6 alkoxy or halogen; and
wherein the chemical bonds which are symbolized with a wiggly line are connected to an optionally substituted alkenylene or alkylene group, respectively, wherein the carbene carbon atom, the two nitrogen atoms and the optionally substituted alkenylene or alkylene group form a ring.

(19) Suitable optional substituents of the optionally substituted alkenylene or alkylene groups are e.g. C.sub.1-10 alkyl, C.sub.3-10 cycloalkyl, alkoxyl, C.sub.3-10 cycloalkoxyl phenyl, or halogen.

(20) The electrons at the carbene carbon atom form a bond with Ru.

(21) In a preferred embodiment, neutral ligand L is a carbene derived from formula 6 or comprising formula 6.

(22) In one embodiment, the neutral ligand L in formula 4 or 5 is a carbene of one of formulas 6a, 6b, 6c or 6d:

(23) ##STR00055##

(24) In formulas 6a to 6d, R.sup.7 and R.sup.8 as defined therein are each independently H, unbranched or branched C.sub.1-20 alkyl, C.sub.5-9 cycloalkyl, or phenyl, wherein the phenyl is optionally substituted with up to three groups independently selected from unbranched or branched C.sub.1-6 alkyl, C.sub.1-6 alkoxy or halogen;

(25) R.sup.9 and R.sup.10 as defined therein are each independently H, unbranched or branched C.sub.1-20 alkyl, or phenyl, wherein the phenyl is optionally substituted with up to three groups independently selected from unbranched or branched C.sub.1-6 alkyl, C.sub.1-6 alkoxy or halogen; or
R.sup.9 and R.sup.10 together with the carbon atoms to which they are attached are combined to form an carbocyclic 3 to 8 membered ring, preferably an aryl ring, more preferably C.sub.6H.sub.4, and
Y and Y′ are halogen.

(26) In one embodiment, the carbene is an unsaturated carbene of formula 6a or 6b, preferably 6a.

(27) In one embodiment, the carbene is unsymmetrically substituted, wherein preferably in formula 6a or 6b R.sup.9═R.sup.10═H and R.sup.7 and R.sup.8 are different.

(28) In one embodiment, L is an unsymmetrical nitrogen-heterocyclic carbene, preferably

(29) ##STR00056##
(n=1-8).

(30) In another embodiment, the electron-donating nitrogen-containing heterocyclic carbene contains only one nitrogen atom.

(31) In one embodiment, the electron-donating carbene is a cyclic (CAAC) or bicyclic (BICAAC) aminoalkyl carbene 7:

(32) ##STR00057##
wherein Ar as defined in formula 7 is aryl, preferably phenyl, optionally substituted with one or more groups selected from: C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perfluoroalkyl, C.sub.1-C.sub.12 alkoxy, C.sub.6-C.sub.14 aryl, C.sub.6-C.sub.14 aryloxy, or halogen; and
wherein the chemical bonds which are symbolized with a wiggly line are connected to an optionally substituted alkenylene or alkylene group, respectively, wherein the carbon atom, the carbene carbon atom, the nitrogen atom and the optionally substituted alkenylene or alkylene group form a ring, which may optionally be bridged by an alkylene group.

(33) Suitable optional substituents of the optionally substituted alkenylene or alkylene groups are e.g. C.sub.1-10 alkyl, C.sub.3-10 cycloalkyl, alkoxyl, C.sub.3-10 cycloalkoxyl phenyl, or halogen.

(34) In one embodiment, the CAAC ligand is of formula 7a

(35) ##STR00058##
wherein each R in formula 7a is independently hydrogen, C.sub.1-C.sub.12 alkyl, C.sub.3-C.sub.12 cycloalkyl, C.sub.2-C.sub.12 alkenyl, C.sub.6-C.sub.14 aryl, C.sub.1-C.sub.5 perfluoroalkyl, C.sub.7-C.sub.24 aralkyl, or C.sub.6-C.sub.14 perfluoroaryl group, which are optionally substituted with at least one C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perfluoroalkyl, C.sub.1-C.sub.12 alkoxy, C.sub.6-C.sub.14 aryloxy, or a halogen atom; and wherein two R which are separated by the C—CR.sub.2—C moiety can be combined with to form a cyclic system

(36) In one embodiment, the CAAC ligand is of formula 7a′

(37) ##STR00059##
wherein R.sup.12, R.sup.13, R.sup.14, and R.sup.15 in formula 7a are each independently hydrogen, C.sub.1-C.sub.12 alkyl, C.sub.3-C.sub.12 cycloalkyl, C.sub.2-C.sub.12 alkenyl, C.sub.6-C.sub.14 aryl, C.sub.1-C.sub.5 perfluoroalkyl, C.sub.7-C.sub.24 aralkyl, or C.sub.6-C.sub.14 perfluoroaryl group, which are optionally substituted with at least one C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perfluoroalkyl, C.sub.1-C.sub.12 alkoxy, C.sub.6-C.sub.14 aryloxy, or a halogen atom; and wherein R.sup.12 and/or R.sup.13 can be combined with R.sup.14 and/or R.sup.15 to form a cyclic system.

(38) In another embodiment, the BICAAC ligand is of formula 7b:

(39) ##STR00060##
wherein each R in formula 7b is independently hydrogen, C.sub.1-C.sub.12 alkyl, C.sub.3-C.sub.12 cycloalkyl, C.sub.2-C.sub.12 alkenyl, C.sub.6-C.sub.14 aryl, C.sub.1-C.sub.5 perfluoroalkyl, C.sub.7-C.sub.24 aralkyl, or C.sub.6-C.sub.14 perfluoroaryl group, which are optionally substituted with at least one C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perfluoroalkyl, C.sub.1-C.sub.12 alkoxy, C.sub.6-C.sub.14 aryloxy, or a halogen atom; and wherein n is 1, 2 or 3; preferably wherein R.sup.16, R.sup.17 and R.sup.18 in formula 7b are each independently hydrogen, C.sub.1-C.sub.12 alkyl, or C.sub.3-C.sub.12 cycloalkyl.

(40) In one embodiment, the BICAAC ligand is of formula 7b′

(41) ##STR00061##
wherein R.sup.16, R.sup.17 and R.sup.18 in formula 7b′ are each independently hydrogen or C.sub.1-C.sub.12 alkyl, or C.sub.3-C.sub.12 cycloalkyl, or C.sub.2-C.sub.12 alkenyl, C.sub.6-C.sub.14 aryl, C.sub.1-C.sub.5 perfluoroalkyl, C.sub.7-C.sub.24 aralkyl, or C.sub.6-C.sub.14 perfluoroaryl group, which are optionally substituted with at least one C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perfluoroalkyl, C.sub.1-C.sub.12 alkoxy, C.sub.6-C.sub.14 aryloxy, or a halogen atom, preferably wherein R.sup.16, R.sup.17 and R.sup.18 in formula 7b′ are each independently hydrogen, C.sub.1-C.sub.12 alkyl, or C.sub.3-C.sub.12 cycloalkyl.

(42) In further embodiments, the CAAC or BICAAC ligand is of one of the following structures 7c to 7k, i.e. a carbene of structure 7c

(43) ##STR00062##
wherein in formula 7c m is an integer of from 0 to 4, and each R.sup.y independently has the meaning of C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perfluoroalkyl, C.sub.1-C.sub.12 alkoxy, C.sub.6-C.sub.14 aryl, C.sub.6-C.sub.14 aryloxy, or halogen; such as a carbene of formula 7c′

(44) ##STR00063##
or is a carbene of formula 7d

(45) ##STR00064##
wherein in formula 7d m is an integer of from 0 to 4, and each R.sup.y independently has the meaning of C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perfluoroalkyl, C.sub.1-C.sub.12 alkoxy, C.sub.6-C.sub.14 aryl, C.sub.6-C.sub.14 aryloxy, or halogen; such as a carbene of formula 7d′

(46) ##STR00065##
or is a carbene of formula 7e

(47) ##STR00066##
or is a carbene of formula 7f

(48) ##STR00067##
or is a carbene of formula 7g or 7h

(49) ##STR00068##
or is a carbene of formula 7i

(50) ##STR00069##
or is a carbene of formula 7k

(51) ##STR00070##
wherein each R in formulas 7c to 7i is independently hydrogen or C.sub.1-C.sub.12 alkyl, or C.sub.3-C.sub.12 cycloalkyl, or C.sub.2-C.sub.12 alkenyl, C.sub.6-C.sub.14 aryl, C.sub.1-C.sub.5 perfluoroalkyl, C.sub.7-C.sub.24 aralkyl, or C.sub.6-C.sub.14 perfluoroaryl group, which are optionally substituted with at least one C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perfluoroalkyl, C.sub.1-C.sub.12 alkoxy, C.sub.5-C.sub.14 aryloxy, or a halogen atom; preferably each R in formulae 7c to 7i is hydrogen, C.sub.1-C.sub.12 alkyl, or C.sub.3-C.sub.12 cycloalkyl.

(52) In one embodiment, in a compound of formula 4 or 5, R.sup.1 is C.sub.1-6 alkyl, optionally substituted with one or more of halogen; or phenyl, optionally substituted with one or more of unbranched or branched C.sub.1-20 alkyl or unbranched or branched C.sub.1-20 alkoxy, C.sub.5-9 cycloalkyl or C.sub.5-9 cycloalkoxy, aryl, aryloxy, unbranched or branched C.sub.1-20 alkylcarbonyl, arylcarbonyl, unbranched or branched C.sub.1-20 alkoxycarbonyl, aryloxycarbonyl, heteroaryl, carboxyl, cyano, nitro, amido, aminosulfonyl, N-heteroarylsulfonyl, unbranched or branched C.sub.1-20 alkylsulfonyl, arylsulfonyl, unbranched or branched C.sub.1-20 alkylsulfinyl, arylsulfinyl, unbranched or branched C.sub.1-20 alkylthio, arylthio, sulfonamide, halogen or N(R.sup.y)(R.sup.z), wherein R.sup.y and R.sup.z are independently selected from H and C.sub.1-20 alkyl.

(53) In one embodiment, R.sup.2 is H.

(54) In another embodiment, —NR.sup.2—C(O)—R.sup.3 is in para-position with respect to O.

(55) In one embodiment, R.sup.3 is methyl or isopropyl.

(56) In one embodiment, R.sup.4 is H.

(57) In one embodiment, R.sup.5 is H.

(58) In one embodiment, R.sup.6, R.sup.7, R.sup.8, and R.sup.9 as defined in formula 4 are independently selected from H and halogen. Preferably, halogen is Cl, Br or F.

(59) In one embodiment, R.sup.10 and R.sup.11 as defined in formula 5 are independently selected from halogen and cyano.

(60) In a preferred embodiment, R.sup.10 and R.sup.11 as defined in formula 5 are cyano.

(61) In one embodiment, L is of formula 6a or 6b.

(62) In a preferred embodiment, R.sup.9 and R.sup.10 as defined in formula 6a or 6b are H, respectively, and R.sup.7 and R.sup.8 as defined in formula 6a and 6b are mesityl, respectively; or 2,6-diisopropylphenyl, or 2,4,6-triisopropylphenyl, respectively.

(63) In another embodiment, R.sup.9 and R.sup.10 as defined in formula 6a or 6b are H, respectively, and R.sup.7 and R.sup.8 as defined in formula 6a and 6b are 2,6-diisopropylphenyl 2,4,6-triisopropylphenyl, respectively, or 2,6-dihalogenophenyl, respectively, or 2,4,6-trihalogenophenyl.

(64) In one embodiment, in a compound of formula 4 or 5, R.sup.1 is C.sub.1-6 alkyl, optionally substituted with one or more of halogen, or phenyl, optionally substituted with one or more of unbranched or branched C.sub.1-20 alkyl, C.sub.5-9 cycloalkyl, unbranched or branched C.sub.1-20 alkoxy, C.sub.5-9 cycloalkoxy, aryl, aryloxy, unbranched or branched C.sub.1-20 alkylcarbonyl, arylcarbonyl, unbranched or branched C.sub.1-20 alkoxycarbonyl, aryloxycarbonyl, heteroaryl, carboxyl, cyano, nitro, amido, aminosulfonyl, N-heteroarylsulfonyl, unbranched or branched C.sub.1-20 alkylsulfonyl, arylsulfonyl, unbranched or branched C.sub.1-20 alkylsulfinyl, arylsulfinyl, unbranched or branched C.sub.1-20 alkylthio, arylthio, sulfonamide, halogen or N(R.sup.y)(R.sup.z), wherein R.sup.y and R.sup.z are independently selected from H and C.sub.1-20 alkyl;

(65) R.sup.2 is H;

(66) R.sup.3 is methyl or isopropyl;

(67) R.sup.4 is H;

(68) R.sup.5 is H;

(69) R.sup.6, R.sup.7, R.sup.8, and R.sup.9 in formula 4 are independently selected from H and halogen;

(70) R.sup.10 and R.sup.11 in formula 5 are independently selected from halogen and cyano;

(71) L is of formula 6a or 6b.

(72) In one embodiment, R.sup.1 is 01-6 alkyl, optionally substituted with one or more of halogen, or phenyl, optionally substituted with one or more of unbranched or branched C.sub.1-20 alkyl, C.sub.5-9 cycloalkyl, unbranched or branched C.sub.1-20 alkoxy, C.sub.5-9 cycloalkoxy, aryl, aryloxy, unbranched or branched C.sub.1-20 alkylcarbonyl, arylcarbonyl, unbranched or branched C.sub.1-20 alkoxycarbonyl, aryloxycarbonyl, heteroaryl, carboxyl, cyano, nitro, amido, aminosulfonyl, N-heteroarylsulfonyl, unbranched or branched C.sub.1-20 alkylsulfonyl, arylsulfonyl, unbranched or branched C.sub.1-20 alkylsulfinyl, arylsulfinyl, unbranched or branched C.sub.1-20 alkylthio, arylthio, sulfonamide, halogen or N(R.sup.y)(R.sup.z), wherein R.sup.y and R.sup.z are independently selected from H and C.sub.1-20 alkyl;

(73) R.sup.2 is H;

(74) NR.sup.2—C(O)—R.sup.3 is in para-position with respect to O;

(75) R.sup.3 is methyl or isopropyl;

(76) R.sup.4 is H;

(77) R.sup.5 is H;

(78) R.sup.6, R.sup.7, R.sup.8, and R.sup.9 in formula 4 are independently selected from H and halogen;

(79) R.sup.10 and R.sup.11 in formula 5 are independently selected from halogen and cyano;

(80) L is of formula 6a or 6b, wherein R.sup.9 and R.sup.10 as defined in formula 6a or 6b are H, respectively, and R.sup.7 and R.sup.8 as defined in formula 6a and 6b are mesityl, 2,6-diisopropyl, or 2,4,6-triisopropyl, respectively.

(81) In one embodiment, the invention relates to compounds E1 to E12 falling under the general formulas 4 or 5

(82) ##STR00071## ##STR00072## ##STR00073##

(83) Preferably, L in E1 and E2 is a NHC ligand.

(84) The amide function —NR.sup.2—C(O)—R.sup.1 in formula 4 and formula 5 can act as a spacer for the introduction of an ion marker (“tag”) for immobilization in an aqueous and/or ion phase as well as on a solid support. Such an ion marking enables better recycling of the catalytic complexes to be performed in aqueous/ion solvents or on a solid support (continuous flow reaction) and thus enables a clear reduction in the cost of the reaction while avoiding contamination of high added value products, in particular in the context of a pharmaceutical molecule synthesis process.

(85) Accordingly, in one embodiment, the compound of formula 4 or 5 is immobilized in an aqueous and/or ion phase or on a solid support.

(86) The invention further relates to a compound of formula 4 or formula 5:

(87) ##STR00074##
wherein the substituents L and R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10 and R.sup.11 have the following meaning:
L is a neutral ligand;
R.sup.1, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10 and R.sup.11 are, independently, H, unbranched or branched C.sub.1-20 alkyl, C.sub.5-9 cycloalkyl, unbranched or branched C.sub.1-20 alkoxy, C.sub.5-9 cycloalkoxy; optionally bearing one or more halogen atoms, respectively; or
aryl, optionally substituted with one or more of unbranched or branched C.sub.1-20 alkyl, C.sub.5-9 cycloalkyl, unbranched or branched C.sub.1-20 alkoxy, aryl, aryloxy, unbranched or branched C.sub.1-20 alkylcarbonyl, arylcarbonyl, unbranched or branched C.sub.1-20 alkoxycarbonyl, aryloxycarbonyl, heteroaryl, carboxyl, cyano, nitro, amido, aminosulfonyl, N-heteroarylsulfonyl, unbranched or branched C.sub.1-20 alkylsulfonyl, arylsulfonyl, unbranched or branched C.sub.1-20 alkylsulfinyl, arylsulfinyl, unbranched or branched C.sub.1-20 alkylthio, arylthio, sulfonamide, halogen, or N(R.sup.y)(R.sup.z), wherein R.sup.y and R.sup.z are independently selected from H and C.sub.1-20 alkyl;
R.sup.2 is H, or unbranched or branched C.sub.1-20 alkyl.

(88) In one embodiment,

(89) R.sup.1 is H, unbranched or branched C.sub.1-20 alkyl, C.sub.5-9 cycloalkyl, unbranched or branched C.sub.1-20 alkoxy or C.sub.5-9 cycloalkoxy; optionally bearing one or more halogen atoms, respectively; or

(90) aryl or aryloxy, optionally substituted with one or more of unbranched or branched C.sub.1-20 alkyl, C.sub.5-9 cycloalkyl, unbranched or branched C.sub.1-20 alkoxy, C.sub.5-9 cycloalkoxy, aryl, aryloxy, unbranched or branched C.sub.1-20 alkylcarbonyl, arylcarbonyl, unbranched or branched C.sub.1-20 alkoxycarbonyl, aryloxycarbonyl, heteroaryl, carboxyl, cyano, nitro, amido, N(R.sup.y)(R.sup.z), wherein R.sup.y and R.sup.z are independently selected from H and C.sub.1-20 alkyl, aminosulfonyl, N-heteroarylsulfonyl, unbranched or branched C.sub.1-20 alkylsulfonyl, arylsulfonyl, unbranched or branched C.sub.1-20 alkylsulfinyl, arylsulfinyl, unbranched or branched C.sub.1-20 alkylthio, arylthio, sulfonamide, or halogen;
R.sup.2 is H, unbranched or branched C.sub.1-20 alkyl;
R.sup.3 is H, unbranched or branched C.sub.1-20 alkyl, or aryl;
R.sup.4 is H, unbranched or branched C.sub.1-20 alkyl, or aryl;
R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10 and R.sup.11 are, independently, H, unbranched or branched C.sub.1-20 alkyl, C.sub.5-9 cycloalkyl, unbranched or branched C.sub.1-20 alkoxy or C.sub.5-9 cycloalkoxy, optionally bearing one or more halogen atoms, respectively; or
Aryl or aryloxy, optionally substituted with one or more of unbranched or branched C.sub.1-20 alkyl, C.sub.5-9 cycloalkyl, unbranched or branched C.sub.1-20 alkoxy, C.sub.5-9 cycloalkoxy, aryl, aryloxy, unbranched or branched C.sub.1-20 alkylcarbonyl, arylcarbonyl, unbranched or branched C.sub.1-20 alkoxycarbonyl, aryloxycarbonyl, heteroaryl, carboxyl, cyano, nitro, amido, aminosulfonyl, N-heteroarylsulfonyl, unbranched or branched C.sub.1-20 alkylsulfonyl, arylsulfonyl, unbranched or branched C.sub.1-20 alkylsulfinyl, arylsulfinyl, unbranched or branched C.sub.1-20 alkylthio, arylthio, sulfonamide, halogen or N(R.sup.y)(R.sup.z), wherein R.sup.y and R.sup.z are independently selected from H and C.sub.1-20 alkyl.

(91) In an alternative aspect, the invention relates to a compound of formula 4 or formula 5

(92) ##STR00075##
wherein in formula 4 or formula 5 the substituents L and R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10 and R.sup.11 have the following meaning:
L is a neutral ligand;
R.sup.1, R.sup.2, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10 and R.sup.11 are, independently, a hydrogen, a C.sub.1 to C.sub.6 alkyl, a C.sub.1 to C.sub.6 perhalogenoalkyl, a residue of an aldehyde, a residue of a ketone, a residue of an ester, a residue of an amide, a nitrile, a cyano, an optionally substituted aryl, a pyridinium alkyl, a pyridinium perhalogenoalkyl or an optionally substituted C.sub.5 or C.sub.6 cyclohexyl, a C.sub.nH.sub.2nY or C.sub.nF.sub.2nY radical with n being between 1 and 6 and Y being an ion marker;
R.sup.2 can also be hydrogen or a C.sub.1 to C.sub.6 alkyl;
R.sup.3 is a C.sub.1 to C.sub.6 alkyl or a C.sub.5 or C.sub.6 cycloalkyl or a C.sub.5 or C.sub.6 aryl;
R.sup.4 is independently, hydrogen, a C.sub.1 to C.sub.6 alkyl, a C.sub.1 to C.sub.6 perhalogenoalkyl, or a C.sub.5 or C.sub.6 aryl.

(93) In a further aspect, the invention relates to a compound of formula I-c:

(94) ##STR00076##
wherein:
each of R.sup.6 and R.sup.7 is independently R, —CN, halogen, —OR, —OC(O)R, —OSiI.sub.3, —SR, —S(O)R, —S(O).sub.2R, —NO.sub.2, —N(R′).sub.2, —NR′C(O)R, —NR′C(O)OR, —NR′C(O)N(R′).sub.2, —NR′SO.sub.2R, —NR′SO.sub.2N(R′).sub.2, —NR′OR, —SeR, —SiI.sub.3, or R.sup.6 and R.sup.7 are optionally taken together with their intervening atoms to form an optionally substituted 3-10 membered, saturated, partially unsaturated or aryl monocyclic or bicyclic ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or
wherein the compound has the structure of formula I-d:

(95) ##STR00077##
or wherein the compound has the structure of formula I-e:

(96) ##STR00078##
or wherein the compound has the structure of formula I-f:

(97) ##STR00079##
wherein
R.sup.1 is a nitrogen-containing heterocyclic carbene (NHC) containing at least two nitrogen atoms or a cyclic aminoalkyl carbene (CAAC) or a bicyclic aminoalkyl carbene (BICAAC) as defined with respect to L in the first aspect above;
r is 1 or 2, preferably 1;
X and Y are —S—;
Ring A is an optionally substituted ring selected from phenyl, an 8-10 membered bicyclic aryl ring, a 5-6 membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or an 8-10 membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur;
each R.sup.x is independently halogen, R, —CN, —C(O)N(R′).sub.2, —C(O)R, —C(O)OR, —OR, —OC(O)R, —OC(O)OR, —OC(O)N(R′).sub.2, —OSiI.sub.3, —N(R′).sub.2, —N(R′).sub.3+, —NR′C(O)R, —NR′C(O)OR, —NR′C(O)N(R′).sub.2, —NR′SO.sub.2R, —NR′SO.sub.2N(R′).sub.2, —NR′OR, —NO.sub.2, —SiI.sub.3, —PI.sub.2, —P(O)I.sub.2, —P(O)(OR).sub.2, —SR, —SC(O)R, —S(O)R, —SO.sub.2R, —SO.sub.3R, —SO.sub.2N(R′).sub.2, or —SeR;
each R′ is independently R, —C(O)R, —C(O)NI.sub.2, —C(O)OR, —SO.sub.2R, —SO.sub.2NI.sub.2, —P(O)(OR).sub.2, or —OR; and
each R is independently hydrogen or an optionally substituted group selected from C.sub.1-20 aliphatic, C.sub.1-20 heteroaliphatic, phenyl, a 3-7 membered saturated or partially unsaturated carbocyclic ring, an 8-10 membered bicyclic saturated, partially unsaturated or aryl ring, a 5-6 membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 3-7 membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 7-10 membered bicyclic saturated or partially unsaturated heterocyclic ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or an 8-10 membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or:
two R groups are optionally taken together with their intervening atoms to form an optionally substituted 3-10 membered, saturated, partially unsaturated, or aryl ring having, in addition to the intervening atoms, 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur;
m is 0-6;
R.sup.2 is R.sup.x;
R.sup.3 is hydrogen or an optionally substituted group selected from C.sub.1-20 aliphatic, C.sub.1-20 heteroaliphatic, phenyl, a 3-7 membered saturated or partially unsaturated carbocyclic ring, a 5-6 membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or a 3-7 membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and
Z is —O— or —S—.

(98) In one embodiment, the compound has the structure of formula I-g:

(99) ##STR00080##

(100) In one embodiment, the compound is not a compound of formula 4 or formula 5 as defined in the first aspect,

(101) ##STR00081##
wherein in formula 4 or formula 5 the substituents L and R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10 and R.sup.11 have the following meaning:
L is: a neutral ligand;
R.sup.1 is: H;
unbranched or branched C.sub.1-20 alkyl or unbranched or branched C.sub.1-20 alkoxy; C.sub.5-9 cycloalkyl or C.sub.5-9 cycloalkoxy; optionally bearing one or more halogen atoms, respectively; or
aryl or aryloxy; optionally substituted, respectively, with one or more of unbranched or branched C.sub.1-20 alkyl or unbranched or branched C.sub.1-20 alkoxy, C.sub.5-9 cycloalkyl or C.sub.5-9 cycloalkoxy, aryl, aryloxy, unbranched or branched C.sub.1-20 alkylcarbonyl, arylcarbonyl, unbranched or branched C.sub.1-20 alkoxycarbonyl, aryloxycarbonyl, heteroaryl, carboxyl, cyano, nitro, amido, aminosulfonyl, N-heteroarylsulfonyl, unbranched or branched C.sub.1-20 alkylsulfonyl, arylsulfonyl, unbranched or branched C.sub.1-20 alkylsulfinyl, arylsulfinyl, unbranched or branched C.sub.1-20 alkylthio, arylthio, sulfonamide, halogen or N(R.sup.y)(R.sup.z), wherein R.sup.y and R.sup.z are independently selected from H and C.sub.1-20 alkyl;
R.sup.2 is: H; unbranched or branched C.sub.1-20 alkyl; aryl; —C(O)R.sup.12; —C(O)OR.sup.12, —C(O)C(O)R.sup.12; —C(O)C(O)OR.sup.12, wherein R.sup.12 has the meaning of C.sub.1-20 alkyl or aryl, respectively; R.sup.12 optionally bearing one or more halogen atoms;
R.sup.3 is: unbranched or branched C.sub.1-20 alkyl; aryl; or
R.sup.13—C(O)—CHR.sup.14, wherein R.sup.13 is C.sub.1-20 alkoxy and R.sup.14 is H or C.sub.1-20 alkyl; or wherein R.sup.13 is C.sub.1-20 alkoxy and R.sup.14 is C(O)—O—C.sub.1-20 alkyl; or wherein R.sup.13 is C.sub.1-20 alkyl and R.sup.14 is H; or R.sup.13 is OH and R.sup.14 is H or C.sub.1-20 alkyl; or
R.sup.15—O—N(R.sup.16)—C(O)—CHR.sup.17, wherein R.sup.15, R.sup.16, and R.sup.17 are independently H or C.sub.1-20 alkyl;
R.sup.4 is: H;
R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10 and R.sup.11 are, independently, H; unbranched or branched C.sub.1-20 alkyl or unbranched or branched C.sub.1-20 alkoxy; C.sub.5-9 cycloalkyl or C.sub.5-9 cycloalkoxy; aryl; aryloxy; unbranched or branched C.sub.1-20 alkylcarbonyl; arylcarbonyl; unbranched or branched C.sub.1-20 alkoxycarbonyl; aryloxycarbonyl; heteroaryl; carboxyl; cyano; nitro; amido; aminosulfonyl; N-heteroarylsulfonyl; unbranched or branched C.sub.1-20 alkylsulfonyl; arylsulfonyl; unbranched or branched C.sub.1-20 alkylsulfinyl; arylsulfinyl; unbranched or branched C.sub.1-20 alkylthio; arylthio; sulfonamide; halogen; or N(R.sup.y)(R.sup.z), wherein R.sup.y and R.sup.z are independently selected from H and C.sub.1-20 alkyl; or
aryl or aryloxy, respectively substituted with one or more of unbranched or branched C.sub.1-20 alkyl or unbranched or branched C.sub.1-20 alkoxy, C.sub.5-9 cycloalkyl or C.sub.5-9 cycloalkoxy, aryl, aryloxy, unbranched or branched C.sub.1-20 alkylcarbonyl, arylcarbonyl, unbranched or branched C.sub.1-20 alkoxycarbonyl, aryloxycarbonyl, heteroaryl, carboxyl, cyano, nitro, amido, aminosulfonyl, N-heteroarylsulfonyl, unbranched or branched C.sub.1-20 alkylsulfonyl, arylsulfonyl, unbranched or branched C.sub.1-20 alkylsulfinyl, arylsulfinyl, unbranched or branched C.sub.1-20 alkylthio, arylthio, sulfonamide, halogen or N(R.sup.y)(R.sup.z), wherein R.sup.y and R.sup.z are independently selected from H and C.sub.1-20 alkyl; and
wherein in formula 4 or 5 the neutral ligand L is a nitrogen-containing carbene containing the moiety of formula 7

(102) ##STR00082##
wherein Ar as defined in formula 7 is aryl, preferably phenyl, optionally substituted with one or more groups selected from: C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perfluoroalkyl, C.sub.1-C.sub.12 alkoxy, C.sub.6-C.sub.14 aryl, C.sub.6-C.sub.14 aryloxy, or halogen; and
wherein the chemical bonds which are symbolized with a wiggly line are connected to an optionally substituted alkenylene or alkylene group, respectively, wherein the carbon atom, the carbene carbon atom, the nitrogen atom and the optionally substituted alkenylene or alkylene group form a ring, which may optionally be bridged by an alkylene group.

(103) Compounds according to the invention may be prepared according to methods which are described in the Example section below. Some of said methods are known in the art.

(104) E.g., in one embodiment, a suitable thiocatechol zinc salt or a suitable ethane 1,2-dithiol zinc salt is reacted with a suitable dichloro ruthenium precursor complex to afford a compound of general formula 4 or 5.

(105) Thiocatechole and ethane 1,2-dithiols are known in the art or may be prepared according to known methods.

(106) Dichloro ruthenium complexes are also known in the art or may be prepared according to known methods.

(107) NHC carbenes of formula 6, e.g. 6a to 6d, are known in the art and may be prepared according to known methods (see e.g. prior art as referred to in the Background section)

(108) CAAC carbenes of formula 7 such as 7a are known in the art and may be prepared according to known methods (see e.g. WO 2017/055945 A1 Eur. J. Inorg. Chem. 2017, 3362-3375; ACS Catal. 2017, 5443-5449; Angew. Chem. Int. Ed. 2015, 54, 1919-1923).

(109) BICAAC carbenes of formula 7b are known in the art and may be prepared according to known methods (see e.g. J. Am. Chem. Soc. 2017, 139, 7753-7756).

(110) The new ruthenium complexes may be used for catalysing a metathesis reaction. Preferably, the metathesis reaction is a metathesis reaction of one or more olefins.

(111) Accordingly, in a second aspect, the invention relates to a method of catalysing a metathesis reaction, comprising providing a compound as defined in the first aspect.

(112) In one embodiment, the method further comprises providing one or more olefins, wherein more than 80% of the olefins formed in the catalysed metathesis reaction are Z-olefins.

(113) In a preferred embodiment, more than 85% or more than 90% or more than 95% of the olefins formed in the catalysed metathesis reaction are Z-olefins.

EXAMPLES

(114) Preparation of Thiocatecholate Zinc Salts

(115) Suitable thiocatecholate zinc salts in the form of complexes may be prepared by reacting an aryl 1,2-dithiol with ethylenediamine in the presence of a zinc salt such as zinc acetate:

3,6-Dichlorobenzene-1,2-dithiolate Zinc 10

(116) ##STR00083##

(117) A mixture of 3,6-dichlorobenzene-1,2-dithiol (7, 211 mg, 1.00 mmol, 1.00 equiv) purchased from Aldrich, Zn(Oac).sub.2.2H.sub.2O (9, 878 mg, 4.00 mmol, 4.00 equiv) and ethylenediamine (8, 0.40 mL, 6.00 mmol, 6.00 equiv) in i-PrOH (8 mL) was allowed to stir for one hour at 22° C. The precipitated solid was filtered, washed with methanol (5.0 mL) and hot chloroform (5.0 mL), and dried in a vacuum desiccator overnight to afford 10 (261 mg, 0.95 mmol, 95% yield) as white solid.

(118) Suitable aryl 1,2-thiolates may be prepared by reacting a suitable arene with sulfur in the presence of a strong base such as an alkyl lithium:

3,4,5,6-Tetrafluorobenzene-1,2-dithiolate Zinc 15

(119) ##STR00084##

(120) To a stirred solution of n-BuLi (12, 0.69 mL, 1.10 mmol, 1.10 equiv) in tetrahydrofuran (2 mL) at −78° C. was added 1,2,3,4-tetrafluorobenzene (11, 150 mg, 1.00 mmol, 1.00 equiv) over 30 minutes, after which the solution was allowed to stir for 45 minutes at −78° C. Then, powdered anhydrous sulfur (13, 35.3 mg, 1.10 mmol, 1.10 equiv) was added in portions over 30 minutes followed by vigorous stirring for 30 minutes at −78° C. Then a solution of n-BuLi (12, 0.69 mL, 1.10 mmol, 1.10 equiv) in hexane (0.5 mL) at −78° C. was added followed by powdered anhydrous sulfur (13, 35.3 mg, 1.10 mmol, 1.10 equiv) in portions over 30 minutes then stirring for 30 minutes at −78° C. The reaction was quenched with cold 6M HCl (1.5 mL) and extracted with Et.sub.2O (3×5.0 mL). The combined organic layers were washed with water (10 mL), dried over anhydrous MgSO.sub.4, and filtered and concentrated in vacuo to give (150.0 mg, 0.82 mmol, 82% yield) 3,4,5,6-tetrafluorobenzene-1,2-dithiol 14 as yellow oil.

(121) In a subsequent step, 3,4,5,6-tetrafluorobenzene-1,2-dithiol 14 is converted to a zinc complex 15

(122) ##STR00085##

(123) A mixture of dithiol 14 (471 mg, 2.20 mmol, 1.00 equiv), Zn(Oac).sub.2.2H.sub.2O (9, 1932 mg, 8.80 mmol, 4.00 equiv) and ethylenediamine (8, 0.88 mL, 13.20 mmol, 6.00 equiv) in i-PrOH (16 mL) was allowed to stir for three hours at 22° C. The precipitated solid was filtered, washed with methanol (5.0 mL) and hot chloroform (5.0 mL), and dried in a vacuum desiccator overnight to afford 3,4,5,6-tetrafluorobenzene-1,2-dithiolate Zinc 15 (470 mg, 1.39 mmol, 63% yield) as white solid.

Preparation of Ru Complexes According to the Invention Using Suitable Ru Precursor Complexes

(124) The Ru precursors are known from the prior art as e.g. referred to in the Background section or may be produced according to known methods.

(125) General procedure for the synthesis of dithiolate Ru complexes:

(126) The reaction according to the general procedure is schematically shown in the following scheme using a Ru dichloro complex bearing a NHC ligand containing two nitrogen atoms which is reacted with a suitable dithiolate complex to afford a compound E6 according to the invention:

(127) ##STR00086##

(128) To a 4 mL vial charged with stir bar and zinc dithiolate 10 or 15 (0.098 mmol, 2.00 equiv) under N.sub.2 atmosphere, a solution of dichloro ruthenium complex (0.049 mmol, 1.00 equiv) in tetrahydrofuran (650 μL) was added and allowed to stir at 22° C. Reaction progress was monitored by .sup.1H NMR spectroscopy. Upon >97% conversion after two to five hours, the solvent was evaporated under vacuum. Residual tetrahydrofuran was removed through co-evaporation with dichloromethane (2×2 mL). The obtained solid was dissolved in dichloromethane and filtered. After removal of dichloromethane from the filtrate, complexes were isolated as green solids.

(129) Ruthenium complex E6 was synthetized according to the general procedure and isolated in the form of a green solid (35 mg, 0.04 mmol, 57% yield). .sup.1H-NMR (C6D6): δ=1.46 (d, 3H, CH.sub.3CHCH.sub.3), 1.69 (br, 6H, CH.sub.3 Mes), 1.75 (d, 3H, CH.sub.3CHCH.sub.3), 2.17 (s, 6H, CH.sub.3 Mes), 2.54 (s, 6H, CH.sub.3 Mes), 3.98 (br, 4H, CH.sub.2 NHC), 5.41 (sept, 1H, CH.sub.3CHCH.sub.3), 6.25 (br, 1H, CH Mes), 6.60 (br, 1H, CH Mes), 6.96 (br, 2H, CH Mes), 6.80 (d, J=2.3 Hz, 1H, C6-H), 7.27 (d, J=9.0 Hz, 1H, C3-H), 7.78 (dd, J=2.3 Hz, 9.0 Hz, 1H, C4-H), 10.11 (s, 1H, NH), 14.30 ppm (s, 1H, Ru=CH).

(130) .sup.19F-NMR (C.sub.6D.sub.6): δ=−76.4 (s), −139.8 (ddd), −144.8 (ddd), −166.4 (ddd), −167.3 ppm (ddd).

(131) .sup.13C-NMR (C.sub.6D.sub.6): δ=19.9 (CH.sub.3 Mes), 21.5 (CH.sub.3CHCH.sub.3), 23.8 (CH.sub.3CHCH.sub.3), 52.8 (CH.sub.2 NHC), 84.0 (CH.sub.3CHCH.sub.3), 116.8 (C6), 117.0 (C3), 118.6 (C4), 129.8 (CH Mes), 130.0 (CH Mes), 132.7 (C5), 135.5 (C Mes), 137.1 (C Mes), 139.1 (C Mes), 142.6 (01), 152.5 (C2), 251.4 ppm (Ru=CH).

(132) Ruthenium complex E5 was synthetized according to the general procedure

(133) ##STR00087##
and isolated in the form of a green solid (36 mg, 0.04 mmol, 59% yield). .sup.1H-NMR (C.sub.6D.sub.6): δ=1.47 (d, 3H, CH.sub.3CHCH.sub.3), 1.64 (br, 6H, CH.sub.3 Mes), 1.72 (d, 3H, CH.sub.3CHCH.sub.3), 2.17 (s, 6H, CH.sub.3 Mes), 2.55 (br, 6H, CH.sub.3 Mes), 3.97 (br, 4H, CH.sub.2 NHC), 5.40 (sept, 1H, CH.sub.3CHCH.sub.3), 6.30 (br, 1H, CH Mes), 6.50 (br, 1H, CH Mes), 6.94 (br, 2H, CH Mes), 6.72&6.82 (Abq, 2H, C3′-H, C4′-H), 6.77 (d, J=2.3 Hz, 1H, C6-H), 7.24 (d, J=9.0 Hz, 1H, C3-H), 7.77 (dd, J=2.3 Hz, 9.0 Hz, 1H, C4-H), 10.10 (s, 1H, NH), 14.14 ppm (s, 1H, Ru=CH).

(134) .sup.19F-NMR (C.sub.6D.sub.6): δ=−76.4 ppm (s).

(135) .sup.13C-NMR (C.sub.6D.sub.6): δ=19.7 (CH.sub.3 Mes), 20.5 (CH.sub.3CHCH.sub.3), 23.1 (CH.sub.3CHCH.sub.3), 51.2 (CH.sub.2 NHC), 81.3 (CH.sub.3CHCH.sub.3), 115.3 (C3, C6), 118.6 (C4), 120.5 (C3′), 121.9 (C4′), 128.8 (CH Mes), 129.5 (C5′), 130.9 (C2′), 131.3 (C5), 137.9 (C Mes), 141.7 (c1), 142.1 (C1′), 151.4 (C2), 154.1 (C6′), 248.1 ppm (Ru=CH).

(136) Ruthenium complex E7

(137) ##STR00088##
was synthetized according to the general procedure from the particular Ru derivative and isolated in the form of a green solid (100 mg, 0.11 mmol, 76% yield).

(138) .sup.1H-NMR (C.sub.6D.sub.6): δ=0.87 (d, 6H, —CH.sub.3CHCH.sub.3), 1.26 (d, 3H, O—CH.sub.3CHCH.sub.3), 1.37 (d, 3H, O—CH.sub.3CHCH.sub.3), 1.48 (s br, 3H, CH.sub.3 Mes), 1.90 (sept, 1H, CH.sub.3CHCH.sub.3), 2.06 (s, 6H, CH.sub.3 Mes), 2.27 (s br, 3H, CH.sub.3 Mes), 2.45 (s br, 3H, CH.sub.3 Mes), 2.59 (s br, 3H, CH.sub.3 Mes), 3.03 (br, 2H, CH.sub.2 NHC), 3.18 (br, 2H, CH.sub.2 NHC), 3.99 (m, 2H, O—CH.sub.2), 5.34 (sept, 1H, O—CH.sub.3CHCH.sub.3), 5.82 (d, J=2.2 Hz, 1H, C6-H), 6.13 (br, 1H, CH Mes), 6.29 (s, 1H, NH), 6.46 (br, 1H, CH Mes), 6.54 (d, J=9.0 Hz, 1H, C3-H), 6.60 (br, 1H, CH Mes), 6.77 (br, 1H, CH Mes), 6.90&7.01 (Abq, 2H, C3′-H, C4′-H), 7.74 (d br, J=9.0 Hz, 1H, C4-H), 14.47 ppm (s, 1H, Ru=CH).

(139) .sup.13C-NMR (C.sub.6D.sub.6): δ=20.7 (CH.sub.3 Mes), 18.9 (CH.sub.3CHCH.sub.3), 20.7 (O—CH.sub.3CHCH.sub.3), 23.7 (O—CH.sub.3CHCH.sub.3), 28.1 (CH.sub.3CHCH.sub.3), 50.9 (CH.sub.2 NHC), 71.0 (O—CH.sub.2), 81.3 (O—CH.sub.3CHCH.sub.3), 113.7 (C6), 115.4 (C3), 116.5 (C4), 121.9 (C3′), 123.5 (C4′), 129.1 (CH Mes), 129.2 (CH Mes), 129.4 (CH Mes), 129.6 (CH Mes), 130.0 (C5′), 131.9 (C2′), 133.3 (C5), 141.8 (01), 142.2 (C1′), 149.6 (C2), 153.2 (NHCOO), 154.6 (C6′), 250.1 ppm (Ru=CH).

(140) Ruthenium complex E8

(141) ##STR00089##
was synthetized according to the general procedure from the particular Ru derivative and isolated in the form of a green solid (137 mg, 0.15 mmol, 78% yield).

(142) .sup.1H-NMR (C.sub.6D.sub.6): δ=0.88 (d, 6H, CH.sub.3CHCH.sub.3), 1.22 (d, 3H, O—CH.sub.3CHCH.sub.3), 1.35 (d, 3H, O—CH.sub.3CHCH.sub.3), 1.45 (br, 3H, CH.sub.3 Mes), 1.91 (sept, 1H, CH.sub.3CHCH.sub.3), 2.01 (br, 3H, CH.sub.3 Mes), 2.06 (br, 3H, CH.sub.3 Mes), 2.25 (br, 3H, CH.sub.3 Mes), 2.40 (s, 3H, CH.sub.3 Mes), 2.47 (s, 3H, CH.sub.3 Mes), 3.05 (br m, 4H, CH.sub.2 NHC), 3.98 (m, 2H, O—CH.sub.2), 5.41 (sept, 1H, O—CH.sub.3CHCH.sub.3), 5.78 (d, J=2.3 Hz, 1H, C6-H), 6.06 (br, 1H, CH Mes), 6.37 (s, 1H, NH), 6.47 (br, 1H, CH Mes), 6.53 (d, J=9.0 Hz, 1H, C3-H), 6.56 (br, 1H, CH Mes), 6.75 (br, 1H, CH Mes), 7.74 (br d, J=9.0 Hz, 1H, C4-H), 14.63 ppm (s, 1H, Ru=CH).

(143) .sup.13C-NMR (C.sub.6D.sub.6): δ=17.1 (CH.sub.3 Mes), 18.4 (CH.sub.3 Mes), 19.0 (CH.sub.3CHCH.sub.3), 19.3 (CH.sub.3 Mes), 20.0 (CH.sub.3 Mes), 20.7 (CH.sub.3 Mes), 20.7 (CH.sub.3 Mes), 20.9 (O—CH.sub.3CHCH.sub.3), 23.8 (O—CH.sub.3CHCH.sub.3), 51.2 (CH.sub.2 NHC), 71.2 (O—CH.sub.2), 82.3 (O—CH.sub.3CHCH.sub.3), 113.7 (C6), 115.8 (C3), 117.0 (C4), 129.0 (CH Mes), 129.3 (CH Mes), 129.6 (CH Mes), 129.9 (CH Mes), 133.9 (C5), 134.5 (C Mes), 134.7 (C Mes), 135.1 (C Mes), 135.7 (C Mes), 137.0 (C Mes), 138.2 (C Mes), 138.5 (C Mes), 139.1 (C Mes), 142.0 (C1), 149.8 (C2), 153.9 (NHCOO), 252.3 ppm (Ru=CH).

(144) In a further example, the reaction according to the general procedure is schematically shown in the following scheme using a Ru dichloro complex bearing an NHC ligand containing one nitrogen atom (CAAC ligand) which is reacted with a suitable dithiolate complex:

(145) ##STR00090##

(146) Ruthenium complex 24 was synthetized according to the following steps: Compound 22 (106 mg, 0.106 mmol, 1.0 eq) was added under nitrogen to a solution of 23 (35 mg, 0.127 mmol, 1.2 eq) and suspension of CuCl (21 mg, 0.212 mmol, 2 eq) in benzene (5 mL). The reaction mixture was stirred at 60° C. for 60 minutes. After cooling down to room temperature, the mixture was poured onto silica gel and the product was eluted with Et.sub.2O/pentane (3:7 v/v) mixture. Green band was collected and solvents were removed. After drying in high vacuum the green solid 24 was obtained, 30 mg (38%).

(147) .sup.1H-NMR (C.sub.6D.sub.6): δ=0.63 (s, 6H, CH.sub.3 CAAC), 0.71 (s, 3H, CH.sub.3 CAAC), 1.37 (br, 6H, O—CH.sub.3CHCH.sub.3), 1.48 (s br, 3H, CH.sub.3 CAAC), 1.59&2.02 (ABq, 2H, CH.sub.2 CAAC), 2.17 (m, 2H, CH.sub.2 Et), 2.38 (m, 2H, CH.sub.2 Et), 4.50 (sept, 1H, O—CH.sub.3CHCH.sub.3), 6.26 (d br, 1H, C3-H), 7.23 (d br, 1H, C4-H), 7.49 (m, 2H, C.sub.ortho—H Ph), 16.49 ppm (br, 1H, Ru=CH).

(148) .sup.13C-NMR (C.sub.6D.sub.6): δ=15.7 (CH.sub.3 Et), 21.5 (O—CH.sub.3CHCH.sub.3), 25.0 (CH.sub.2 Et), 26.8 (CH.sub.3 CAAC), 27.0 (CH.sub.3 CAAC), 29.4 (CH.sub.3 CAAC), 50.5 (CH.sub.2 CAAC), 60.4 (CCH.sub.3Ph), 74.8 (O—CH.sub.3CHCH.sub.3), 79.8 (NC(CH.sub.3).sub.2), 112.7 (C3), 122.2 (C4), 129.5 (C5), 135.9 (C-Et), 139.6 (N—C.sub.ipso), 140.7 (C2), 143.5 (C1), 145.2 (C.sub.ipso Ph), 247.7 ppm (NC: CAAC).

(149) Ruthenium complex E12 was synthetized according to the general procedure and identified without isolation by the characteristic new alkylidene signal at δ=13.85 ppm (.sup.1H-NMR (CD.sub.2Cl.sub.2)s, Ru=CH):

(150) ##STR00091##

(151) Exemplary Metathesis Reaction

(152) Z-selective cross-metathesis reaction (CM) between allylbenzene 17 and cis-1,4-butendiol-diacetate 18 to yield (Z)-4-phenyl-2-buteneyl-1-acetate 19 (Z-isomer was confirmed by GC standards):

(153) ##STR00092##

(154) A 3 mol % [Ru] catalyst (complexes E5, E6, E7, E8 according to the invention, and complexes 20 or 21 for comparison) (0.0006 mmol, 3.0 mol %) in THF (290 μL) was transferred by syringe to a vial containing 17 (2.4 mg, 0.02 mmol, 1.00 equiv) and 18 (6.9 mg, 0.04 mmol, 2.00 equiv). The resulting mixture was allowed to stir for 9 hours at 22° C. Analysis of the GC-MS chromatogram revealed surprisingly different yields of the substrate 19 with the different [Ru] catalysts, however the corresponding CM product was obtained in each case in >98:2 Z/E ratio.

(155) TABLE-US-00001 20 21 E5 E7 E8 E6 Catalyst Yield of 19 [%] Z/E ratio 20 46 >98:2 21 49 >98:2 E5 54 >98:2 E7 54 >98:2 E8 56 >98:2 E6 58 >98:2

(156) Z-selective cross-metathesis reaction (CM) between oct-1-ene 22 and cis-1,4-butendiol-diacetate 18 to yield (Z)-non-2-en-1-yl acetate 23 (Z-isomer was confirmed by GC standards):

(157) ##STR00099##

(158) A 3 mol % [Ru] catalyst (complexes E5, E7 according to the invention, and complex 21 for comparison) (0.00126 mmol, 3.0 mol %) in THF (290 μL) was transferred by syringe to a vial containing 18 (14.5 mg, 0.084 mmol, 2.00 equiv) and 22 (4.71 mg, 0.042 mmol, 1.00 equiv). The resulting mixture was allowed to stir for 9 hours at 22° C. Analysis of the GC-MS chromatogram revealed surprisingly different yields of the substrate 23 with the different [Ru] catalysts, however the corresponding CM product was obtained in each case in >98:2 Z/E ratio.

(159) TABLE-US-00002 00 21 01 E7 02 E5 Catalyst Yield of 23 [%] Z/E ratio 21 64 >98:2 E7 72 >98:2 E5 74 >98:2

(160) As can be seen from compounds E5, E6, E7 and E8 compared to compound 20 and 21, the omission of the amido group results in a drop of yield of target product. Accordingly, one can draw the conclusion from these results that the introduction of an amide function on the styrenyl ether ligand promotes the activation of the catalyst. Besides the significant activation of the catalyst relatively high conversions in very short amounts of time are observed. Under these conditions, an economic impact can be envisaged by significantly reducing the catalytic load in the metathesis reactions compared to the known catalysts lacking the amido group without affecting the yield.