CYCLIC SUPPORTED CATALYSTS

Abstract

The present invention relates to ligands based on calixarenes, metal complexes including such ligands and their use as homogeneous or heterogeneous catalysts.

Claims

1-17. (canceled)

18. Compound of general formula (I): ##STR00145## in which: n represents an integer from 7 to 20 or greater than 20, or 21 to 220, X is a linear or branched alkyl comprising 1 to 10 carbon atoms, a polyethylene glycol comprising from 1 to 5 units or ethylene glycol (linear or branched alkyl comprising from 0 to 10 carbon atoms)-aryl, or the aryl being selected from phenyl and naphthyl, R.sub.1 represents a linear or branched alkyl comprising 1 to 8 carbon atoms, O-linear or branched alkyl comprising 1 to 8 carbon atoms or O-(straight or branched alkyl of 0-3 carbon atoms)-aryl, M.sup.m+ is a metal in oxidation state m or a metal cluster comprising a plurality of metals in the oxidation state m, where m is 0, 1, 2, 3, 4 or 5, L consists of one or more neutral ligands or negatively charged linked to the metal, and said compound has the formula (IA) in which t is 0 and Z represents a group Q selected from the group consisting of phosphorus ligands, or the phosphonites and phosphinites, with the exception of phosphines and phosphine oxides, N-heterocyclic carbenes, or 1,3-imidazolylidenes, 1,3-imidazolinylidenes, 1,2,4-triazolylidenes, 1,3-benzimidazolylidenes, 1,2,4-triazolylidenes and 1,3-thiazolylidenes, or salen ligands, said compound has the formula (IB) in which t is 0 and Z represents a group Q, a precursor of a group Q selected from the group consisting of azoliums, or 1,3-imidazolium, 1,3-imidazolinium, 1,3-benzimidazolium, 1,2,4-triazolium, 1,3-thiazolium, precursors of phosphorus ligands with the exception of phosphines and phosphine oxides, or chalcogenides, or phosphine sulfides, or salen ligands precursors, or derivatives of salicylaldehyde, said compound has the formula (IC) wherein t is 1 and Z represents a group Q selected from the group consisting of phosphorus ligands, or phosphines, phosphonites, phosphinites, and N-heterocyclic carbenes, or 1,3-imidazolylidenes, 1,3-imidazolinylidenes, 1,2,4-triazolylidenes, 1,3-benzimidazolylidenes, 1,2,4 triazolylidenes and 1,3-thiazolylidenes, or salen ligands.

19. Compound according to claim 18 of general formula (I): ##STR00146## in which: n represents an integer from 7 to 20 or greater than 20, or 21 to 220, X is a linear or branched alkyl comprising 1 to 10 carbon atoms, a polyethylene glycol comprising from 1 to 5 units or ethylene glycol (linear or branched alkyl comprising from 0 to 10 carbon atoms)-aryl, or the aryl being selected from phenyl and naphthyl, R.sub.1 represents a linear or branched alkyl comprising 1 to 8 carbon atoms, O-linear or branched alkyl comprising 1 to 8 carbon atoms or O-(straight or branched alkyl of 0-3 carbon atoms)-aryl, M.sup.m+ is a metal in oxidation state m or a metal cluster comprising a plurality of metals in the oxidation state m, where m is 0, 1, 2, 3, 4 or 5, L consists of one or more neutral ligands or negatively charged linked to the metal, and said compound has the formula (IA) in which t is 0 and Z represents a group Q selected from the group consisting of phosphorus ligands, or the phosphonites and phosphinites, with the exception of phosphines and phosphine oxides, N-heterocyclic carbenes, or 1,3-imidazolylidenes, 1,3-imidazolinylidenes, 1,2,4-triazolylidenes, 1,3-benzimidazolylidenes, 1,2,4-triazolylidenes and 1,3-thiazolylidenes, or, said compound has the formula (IB) in which t is 0 and Z represents a group Q, a precursor of a group Q selected from the group consisting of azoliums, or 1,3-imidazolium, 1,3-imidazolinium, 1,3-benzimidazolium, 1,2,4-triazolium, 1,3-thiazolium, precursors of phosphorus ligands with the exception of phosphines and phosphine oxides, or chalcogenides, or phosphine sulfides, or said compound has the formula (IC) wherein t is 1 and Z represents a group Q selected from the group consisting of phosphorus ligands, or phosphines, phosphonites, phosphinites, and N-heterocyclic carbenes, or 1,3-imidazolylidenes, 1,3-imidazolinylidenes, 1,2,4-triazolylidenes, 1,3-benzimidazolylidenes, 1,2,4 triazolylidenes and 1,3-thiazolylidenes.

20. Compound according to claim 18 of the following general formula (IA): ##STR00147## in which: n represents an integer from 7 to 20 or greater than 20, or 21 to 220, X is a linear or branched alkyl comprising 1 to 10 carbon atoms, a polyethylene glycol comprising from 1 to 5 units or ethylene glycol (linear or branched alkyl comprising from 0 to 10 carbon atoms)-aryl, or the aryl being selected from phenyl and naphthyl, R.sub.1 represents a linear or branched alkyl comprising 1 to 8 carbon atoms, O-linear or branched alkyl comprising 1 to 8 carbon atoms or O-(straight or branched alkyl of 0-3 carbon atoms)-aryl, M.sup.m+ is a metal in oxidation state m or a metal cluster comprising a plurality of metals in the oxidation state m, where m is 0, 1, 2, 3, 4 or 5, Q is selected from the group consisting of phosphorus ligands, or the phosphonites and phosphinites, with the exception of phosphines and phosphine oxides, N-heterocyclic carbenes, or 1,3-imidazolylidenes, 1,3-imidazolinylidenes, 1,2,4-triazolylidenes, 1,3-benzimidazolylidenes, 1,2,4-triazolylidenes and 1,3-thiazolylidenes.

21. Compound according to claim 18 of the following general formula (IC): ##STR00148## in which: n represents an integer from 7 to 20 or greater than 20, or 21 to 220, X is a linear or branched alkyl comprising 1 to 10 carbon atoms, a polyethylene glycol comprising from 1 to 5 units or ethylene glycol (linear or branched alkyl comprising from 0 to 10 carbon atoms)-aryl, or the aryl being selected from phenyl and naphthyl, R.sub.1 represents a linear or branched alkyl comprising 1 to 8 carbon atoms, O-linear or branched alkyl comprising 1 to 8 carbon atoms or O-(straight or branched alkyl of 0-3 carbon atoms)-aryl, Q is selected from the group consisting of phosphorus ligands, or phosphines, phosphonites, phosphinites, and N-heterocyclic carbenes, or 1,3-imidazolylidenes, 1,3-imidazolinylidenes, 1,2,4-triazolylidenes, 1,3-benzimidazolylidenes, 1,2,4-triazolylidenes and 1,3-thiazolylidenes.

22. Compound of formula (I) according to claim 18, wherein the group X is a linear alkyl chain comprising from 2 to 8 or from 3 to 8 carbon atoms, or 2, 3, 4, 5, 6, 7 or 8, or from 2 to 6 or from 3 to 6 carbon atoms, or from 2 to 4 or from 3 to 4 carbon atoms.

23. Compound of formula (I) according to claim 18, wherein the group R.sub.1 is selected from n-octyl, t-butyl, O-benzyl and O-alkyl or O-methyl, O-ethyl, O-propyl, or t-butyl or O-benzyl.

24. Compound of formula (I) according to claim 18, wherein n=8 or 16.

25. Compound of formula (I) according to claim 18, wherein n represents an integer from 7 to 20, X is a linear alkyl having 3 to 6 carbon atoms, t is 0 and Z represents a group Q selected from the group consisting of phosphorus ligands, or phosphonites and phosphinites, with the exception of phosphines and phosphine oxides and N-heterocyclic carbenes, or 1,3-imidazolylidenes, 1,3-imidazolinylidenes, 1,2,4-triazolylidenes, 1,3-benzimidazolylidenes, 1,2,4-triazolylidenes and 1,3-thiazolylidenes, or t is 0 and Z represents a group Q precursor of a group Q, selected from the group consisting of azoliums, or 1,3-imidazolium, 1,3-imidazolinium, 1,3-benzimidazolium, 1,2,4-triazolium, 1,3-thiazolium, precursors of phosphorus ligands with the exception of phosphines and phosphine oxides or chalcogenides, particularly phosphine sulfides, t is 1 and Z represents a group Q selected from the group consisting of phosphorus ligands, or phosphines, phosphonites and phosphinites, and N-heterocyclic carbenes, or 1,3-imidazolylidenes, 1,3-imidazolinylidenes, 1,2,4-triazolylidenes, 1,3-benzimidazolylidenes, 1,2,4-triazolylidenes and 1,3-thiazolylidenes, R.sub.1 represents n-octyl, t-butyl, O-benzyl or O-alkyl or O-methyl, O-ethyl, O-propyl, or t-butyl or O-benzyl, M.sup.m+ is a metal in oxidation state m or a metal cluster comprising a plurality of metals in the oxidation state m, where m is 0, 1, 2, 3, 4 or 5. L consists of one or more neutral ligands or negatively charged linked to the metal.

26. Compound of formula (IC) according to claim 18: ##STR00149## in which: n represents an integer from 7 to 20 or greater than 20, or 21 to 220, X is a linear or branched alkyl comprising 1 to 10 carbon atoms, a polyethylene glycol comprising from 1 to 5 units or ethylene glycol (linear or branched alkyl comprising from 0 to 10 carbon atoms)-aryl, or the aryl being selected from phenyl and naphthyl, R.sub.1 represents a linear or branched alkyl comprising 1 to 8 carbon atoms, O-linear or branched alkyl comprising 1 to 8 carbon atoms or O-(straight or branched alkyl of 0-3 carbon atoms)-aryl, Q is selected from the group consisting of phosphorus ligands, or phosphines, phosphonites, phosphinites, and N-heterocyclic carbenes, or 1,3-imidazolylidenes, 1,3-imidazolinylidenes, 1,2,4-triazolylidenes, 1,3-benzimidazolylidenes, 1,2,4-triazolylidenes and 1,3-thiazolylidenes, M.sup.m+ is a metal in oxidation state m or a metal cluster comprising a plurality of metals in the oxidation state m, where m is 0, 1, 2, 3, 4 or 5, or a transition metal group IB, IIB, IIIB, VA, IVB, VB, VIB, VIIB or VIIIB, or selected from the group consisting of Ni, Pd, Ru, Rh, Cu, Co or Pt, and L consists of one or more neutral ligands or negatively charged linked to the metal.

27. Compound of formula (I) according to claim 18: ##STR00150## in which: n represents an integer from 7 to 20 or greater than 20, or 21 to 220, X is a linear or branched alkyl comprising 1 to 10 carbon atoms, a polyethylene glycol comprising from 1 to 5 units or ethylene glycol (linear or branched alkyl comprising from 0 to 10 carbon atoms)-aryl, the aryl being or selected from phenyl and naphthyl, R.sub.1 represents a linear or branched alkyl comprising 1 to 8 carbon atoms, O-linear or branched alkyl comprising 1 to 8 carbon atoms or O-(straight or branched alkyl of 0-3 carbon atoms)-aryl, M.sup.m+ is a metal in oxidation state m or a metal cluster comprising a plurality of metals in the oxidation state m, where m is 0, 1, 2, 3, 4 or 5, L consists of one or more neutral ligands or negatively charged linked to the metal, and said compound has the formula (IA) in which t is 0 and Z represents a group Q selected from the group consisting of salen ligands, or enantiopure salen ligands, or derivatives of cyclohexyldiamine and diphenylethylene and derivatives of the above salen ligands, said compound has the formula (IB) in which t is 0 and Z represents a group Q, a precursor of a group Q selected from the group consisting of precursors of salen ligands, or derivatives of salicylaldehyde, said compound has the formula (IC) wherein t is 1 and Z represents a group Q selected from the group consisting of salen ligands, or enantiopure salen ligands, or derivatives of cyclohexyldiamine and diphenylethylene and derivatives of the above salen ligands.

28. Compound of formula (I) according to claim 18 selected from: ##STR00151## ##STR00152## ##STR00153##

29. Method of catalyzing a reaction selected from the group consisting of reduction reactions, or reduction reactions in the presence of H.sub.2 or the hydrogenation of carbonyl, alkene, alkyne or arene, the oxidation reactions, or oxidation reactions in the presence of O.sub.2, the carbon-carbon bond forming reactions, or the Suzuki reaction, Heck, Stille, Kumada and Sonogashira, the carbon-heteroatom bond forming reactions, or carbon-nitrogen, carbon-oxygen, carbon-phosphorus, and carbon-sulfur bond formation, carbonylation reactions in the presence CO, or Fischer-Tropsch, the gas phase carboxylation of reactions in the presence of CO.sub.2, and asymmetric catalysis reactions, or the epoxide opening reactions or asymmetric catalysis reactions allowing CC or CX bond formation, wherein the catalyst is a compound of formula (IC): ##STR00154## in which: n represents an integer from 7 to 20 or greater than 20, or 21 to 220, X is a linear or branched alkyl comprising 1 to 10 carbon atoms, a polyethylene glycol comprising from 1 to 5 units or ethylene glycol (linear or branched alkyl comprising from 0 to 10 carbon atoms)-aryl, or the aryl being selected from phenyl and naphthyl, R.sub.1 represents a linear or branched alkyl comprising 1 to 8 carbon atoms, O-linear or branched alkyl comprising 1 to 8 carbon atoms or O-(straight or branched alkyl of 0-3 carbon atoms)-aryl, M.sup.m+ is a metal in oxidation state m or a metal cluster comprising a plurality of metals in the oxidation state m, where m is 0, 1, 2, 3, 4 or 5, L consists of one or more neutral ligands or negatively charged linked to the metal, Z is selected from the group consisting of phosphorus ligands, or phosphines, phosphonites, phosphinites, and N-heterocyclic carbenes, or 1,3-imidazolylidenes, 1,3-imidazolinylidenes, 1,2,4-triazolylidenes, 1,3-benzimidazolylidenes, 1,2,4 triazolylidenes and 1,3-thiazolylidenes, or salen ligands.

30. Method for preparing a compound of formula (IA): ##STR00155## wherein n represents an integer from 7 to 20 or greater than 20, or 21 to 220, X is a linear or branched alkyl comprising 1 to 10 carbon atoms, a polyethylene glycol comprising from 1 to 5 units or ethylene glycol (linear or branched alkyl comprising from 0 to 10 carbon atoms)-aryl, or the aryl being selected from phenyl and naphthyl, R.sub.1 represents a linear or branched alkyl comprising 1 to 8 carbon atoms, O-linear or branched alkyl comprising 1 to 8 carbon atoms or O-(straight or branched alkyl of 0-3 carbon atoms)-aryl, Q is a phosphorus ligand, or a secondary phosphonite, or a secondary phosphinite other than a phosphine and phosphine oxide, or a compound of formula (IB): ##STR00156## wherein n represents an integer from 7 to 20 or greater than 20, or 21 to 220, X is a linear or branched alkyl comprising 1 to 10 carbon atoms, a polyethylene glycol comprising from 1 to 5 units or ethylene glycol (linear or branched alkyl comprising from 0 to 10 carbon atoms)-aryl, or the aryl being selected from phenyl and naphthyl, R.sub.1 represents a linear or branched alkyl comprising 1 to 8 carbon atoms, O-linear or branched alkyl comprising 1 to 8 carbon atoms or O-(straight or branched alkyl of 0-3 carbon atoms)-aryl, wherein Q is selected from the group consisting of azoliums, or 1,3-imidazolium, 1,3-imidazolinium, 1,3-benzimidazolium, 1,2,4-triazolium, 1,3-thiazolium comprising a step of contacting a compound of formula (II): ##STR00157## in which: n represents an integer from 7 to 20 or greater than 20, or 21 to 220, X is a linear or branched alkyl comprising 1 to 10 carbon atoms, a polyethylene glycol comprising from 1 to 5 units or ethylene glycol (linear or branched alkyl comprising from 0 to 10 carbon atoms)-aryl, or the aryl being selected from phenyl and naphthyl, R.sub.1 represents a linear or branched alkyl comprising 1 to 8 carbon atoms, O-linear or branched alkyl comprising 1 to 8 carbon atoms or O-(straight or branched alkyl of 0-3 carbon atoms)-aryl, V represents a leaving group, or chosen from the group consisting of halogens, or Cl, Br and I and sulfonates, or OSO.sub.2Me, OSO.sub.2(C.sub.7H.sub.7) and OSO.sub.2CF.sub.3, with a compound of formula QA wherein Q is selected from the group consisting of phosphorus ligands, or a secondary phosphonite, or secondary, with the exception of phosphines and phosphine oxides and A represents an alkali metal selected from the group consisting of Na, K and Li or a is H and the reaction is carried out in the presence of a base, to give a compound of formula (IA), or with a compound of formula Q selected from the group consisting of azoles, or 1,3-imidazoles, 1,3-imidazoline, 1,3-benzimidazoles, 1,2,4-triazoles and 1,3-thiazoles, or, a compound of formula (IC): ##STR00158## in which: n represents an integer from 7 to 20 or greater than 20, or 21 to 220, X is a linear or branched alkyl comprising 1 to 10 carbon atoms, a polyethylene glycol comprising from 1 to 5 units or ethylene glycol (linear or branched alkyl comprising from 0 to 10 carbon atoms)-aryl, or the aryl being selected from phenyl and naphthyl, R.sub.1 represents a linear or branched alkyl comprising 1 to 8 carbon atoms, O-linear or branched alkyl comprising 1 to 8 carbon atoms or O-(straight or branched alkyl of 0-3 carbon atoms)-aryl, M.sup.m+ is a metal in oxidation state m or a metal cluster comprising a plurality of metals in the oxidation state m, where m is 0, 1, 2, 3, 4 or 5, L consists of one or more neutral ligands or negatively charged linked to the metal, Z represents a group Q selected from the group consisting of phosphines, phosphonites, phosphinites, and N-heterocyclic carbenes, or 1,3-imidazolylidenes, 1,3-imidazolinylidenes, 1,2,4-triazolylidenes, 1,3-benzimidazolylidenes, 1,2,4-triazolylidenes and 1,3-thiazolylidenes, comprising a step of contacting a compound of formula (IA), said compound (IA) has the formula (I) wherein t is 0 and Z represents a group Q selected from the group consisting of phosphorus ligands, or phosphines, phosphonites, phosphinites, and N-heterocyclic carbenes, or 1,3-imidazolylidenes, 1,3-imidazolinylidenes, 1,2,4-triazolylidenes, 1,3-benzimidazolylidenes, 1,2,4-triazolylidenes and 1,3-thiazolylidenes, ##STR00159## with a metal complex of formula (L)M.sup.n+ where M.sup.m+ is a metal in oxidation state m or a metal cluster comprising a plurality of metals in the oxidation state m, where m is 0, 1, 2, 3, 4 or 5, or 0, 1, 2 or 3, and L is comprised of 0, one or more neutral or negatively charged ligands bound to the metal.

31. Method according to claim 30 for preparing a compound of formula (IC): ##STR00160## in which: n represents an integer from 7 to 20 or greater than 20, or 21 to 220, X is a linear or branched alkyl comprising 1 to 10 carbon atoms, a polyethylene glycol comprising from 1 to 5 units or ethylene glycol (linear or branched alkyl comprising from 0 to 10 carbon atoms)-aryl, the aryl being or selected from phenyl and naphthyl, R.sub.1 represents a linear or branched alkyl comprising 1 to 8 carbon atoms, O-linear or branched alkyl comprising 1 to 8 carbon atoms or O-(straight or branched alkyl of 0-3 carbon atoms)-aryl, M.sup.m+ is a metal in oxidation state m or a metal cluster comprising a plurality of metals in the oxidation state m, where m is 0, 1, 2, 3, 4 or 5, L consists of one or more neutral ligands or negatively charged linked to the metal Q is selected from the group consisting of salen ligands, or enantiopure salen ligands, or derivatives of cyclohexyldiamine and diphenylethylene and derivatives of the above salen ligands, comprising a step of contacting a compound of formula (II): ##STR00161## in which: V represents a leaving group, or chosen from the group consisting of halogens, or Cl, Br and I and sulfonates, or OSO.sub.2Me, OSO.sub.2(C.sub.7H.sub.7) et OSO.sub.2CF.sub.3, with a precursor of a grafting group of a group Q, particularly sodium azide, Q represents a group selected from the salen ligand precursor group, or derivatives of salicylaldehyde and or the 3-(tert-butyl)-5-triazol-2-hydroxybenzaldehyde, to obtain a compound of formula (VIII) ##STR00162## in which: G represents a grafting group of said group Q, or a N.sub.3 group, and comprising a step of contacting said compound of formula (VIII) with said group Q to obtain a compound of formula (IB) ##STR00163## then comprising a step of contacting said compound of formula (IB), with another precursor group of the salen ligand, or derivatives of salicylaldehyde and or the compound of formula (VII), ##STR00164## to obtain a compound of formula (IA), ##STR00165## and comprising a step of contacting said compound of formula (IA), with a metal complex of formula LM.sup.m+, wherein: M.sup.m+ is a metal in oxidation state m or a metal cluster comprising a plurality of metals in the oxidation state m, where m is 0, 1, 2, 3, 4 or 5, L consists of one or more neutral ligands or negatively charged linked to the metal, optionally in the presence of a base, or with cobalt acetate and para-toluenesulfonic acid, to obtain said compound of formula (IC).

32. Method according to claim 29, wherein said compound of formula (IC) is used as heterogeneous catalyst.

33. Method according to claim 29, wherein the leaching ratio of metal of said catalyst is less than 10%, or less than 5% of the total weight of the metal content in this catalyst.

34. Method according to claim 29, wherein said compound of formula (IC) is used as heterogeneous catalyst, and wherein the leaching ratio of metal of said catalyst is less than 10%, or less than 5% of the total weight of the metal content in this catalyst.

Description

EXAMPLES

[0283] The four schemes below illustrate the synthesis of the catalysts according to the present invention containing a N-heterocyclic carbene or phosphine:

##STR00052##

##STR00053##

##STR00054##

##STR00055## ##STR00056##

Example 1: Preparation of the Chlorinated Precursors

Preparation of Calixarene 2

[0284] Benzyloxyphenol 1 (200 g, 1 mol), paraformaldehyde (78.7 g) and xylene (2 L) were loaded, and the medium was placed under argon. t-BuOK (7.39 g, 65.9 mmol) was loaded and vacuum-argon cycles were performed. The mixture was brought to reflux for 8 hours under strong stirring, collecting the water formed with a Dean-Stark water separating apparatus. The mixture was allowed to cool to room temperature and the xylene was evaporated under reduced pressure. The solid residue was heated at 45 C. in 3 L of THF under vigorous stirring, filtered and rinsed with 500 ml of THF. The cake was dispersed with vigorous stirring in 2.5 L of THF at 45 C. for 30 min. 1 L of THF was evaporated and a solution of THF/HCl (33%) (200/50 ml) was added. The mixture was stirred for 30 min at room temperature, filtered and rinsed with 250 ml of THF. The product was allowed to dry overnight under air and then a few hours using a rotary vane pump, after grinding. 169.5 g of very pure product was obtained (yield: 80%). .sup.1H NMR (DMSO-d6, ppm): 8.67 (s, 8H), 7.30 (m, 40H), 6.58 (s, 16H), 4.80 (s, 16H); 3.77 (s, 16H). m/z (MALDI, matrice DHB): 1719.62 [M+Na.sup.+] (calc=1697.67).

Preparation of Calixarene 3

[0285] Ground benzyloxycalix[8]arene 2 (60 g, 35.3 mmol) was loaded, then, 1-bromo-4-chlorobutane (520 ml, 3 mol) and DMF (90 ml) were added under argon. The mixture was heated to 40 C., stirring was stopped and a third of the sodium hydride (22.6 g, 5.65.10.sup.1 mol) was added. The mixture was placed under argon and stirring was gradually started. The rest of the sodium hydride was added in two fractions, spacing each addition by 1 h30. The mixture was allowed to react at 30 C. until the next morning. 350 ml of dichloromethane was added, the mixture was filtered over Celite, rinsed with 200 ml of dichloromethane and the solvents are evaporated at 60 C. under reduced pressure. 2 L of methanol was added and the solid was dispersed with vigorous stirring for 24 hours. The mixture was filtered, and the cake was dried several hours in air and then to the vane pump. 2 L of ethanol is added and the solid is dispersed with vigorous stirring for 24 hours. The mixture was filtered, and the cake was dried several hours in air and then using a rotary vane pump. 80 g of a pure white solid was obtained (yield=93%). .sup.1H NMR (DMSO-d6, ppm): 7.15 (m, 40H), 6.51 (s, 16H), 4.69 (s, 16H), 3.89 (s, 16H), 3.56 (m, 16H), 3.47 (t, 16H, .sup.3J(H,H)=6.4 Hz), 1.75 (m, 16H), 1.65 (m, 16H). .sup.13C NMR (DMSO-d6, ppm): 155.17, 149.83, 138.08, 135.67, 129.34, 128.74, 128.64, 115.75, 73.38, 70.26, 46.29, 30.91, 30.20, 28.35. m/z (ESI, DCM-isopropanol, positive mode): 2439.85 [M+Na.sup.+].

Example 2: Preparation of Phosphorus Ligands

Phosphorus Ligand 4

[0286] Calixarene 3 (10 g, 4.13 mmol) was loaded in a reactor, dried under vacuum for 30 min, followed by addition of THF (17 ml) under argon. The solution was cooled to 20 C. and a solution of KPPh.sub.2 (70.2 ml, 0.5 M in THF, 35.1 mmol) was slowly added. The solution was stirred at room temperature for 4 h, followed by addition of DCM (20 ml). The mixture was filtered through celite and rinsed with DCM. The filtrate is evaporated to dryness and the residue was triturated with diethyl ether and filtered. The cake was triturated with pentane and filtered. The product was dried under vacuum and to obtain 14.2 g of a pale yellow product (yield: 95%). .sup.1H NMR (CDCl.sub.3, ppm): 7.39 to 7.33 (m, 40H), 7.26 to 7.23 (m, 40H), 7.00 (s, 30H), 6.45 (s, 16H), 4.43 (s, 16H), 3.88 (s, 16H), 3.60 (m, 16H), 2.09 to 1.97 (m, 16H), 1, 78 (m, 16H), 1, 57 (m, 16H). .sup.31P NMR (CDCl.sub.3, ppm): 16.33 (s).

Example 3: Preparation of Imidazolium Salts (Precursors of Heterocyclic N-Carbene Ligands)

Ligand IMes.HCl 5

[0287] Calixarene 3 (10.1 g, 4.2 mmol) and mesitylimidazole (25 g, 134.2 mmol) were loaded. The reactor was placed under an argon atmosphere and then anhydrous DMF was added (200 ml). 3 vacuum/argon were performed, and the mixture was heated for 7-9 days at 100 C. with stirring (the reaction was monitored by NMR). DMF was evaporated and the product is dissolved in DCM (200 ml) and precipitated with ether (300 ml). The resulting brown solid was washed with diethyl ether (300 ml), triturated with diethyl ether (100 ml) and filtered. 15.5 g of a brown solid were obtained (yield=97%). .sup.1H NMR (DMSO-d6, ppm): 10.04 (s, 8H), 8.21 (s, 8H), 7.95 (s, 16H), 7.06 (s, 56H), 6.48 (s, 16H), 4.61 (s, 16H), 4.39 (s, 16H), 3.89 (s, 16H), 3.71 (s, 16H), 2.89 (s, 32H), 2.73 (s, 32H), 2.28 (s, 24H), 2.03 (s, 16H), 1.66 (s, 48H), 1.65 (s, 16H). m/z (ESI, positive mode): 942.49 [M+4Na.sup.+]/4 (calc=942.50) 1268.31 [M+3Na.sup.+]/3 (calc=1268.48), 1920.45 [M+2Na.sup.+]/2 (calc=1920.45).

Ligand IPr.HBr 6

[0288] Calixarene 3 (3 g, 1.24 mmol), diisopropylimidazole (4.24 g, 18.57 mmol) and sodium bromide (12.65 g, 124 mmol) were placed in a reactor under argon. 30 ml of anhydrous DMF was added. 3 vacuum/argon were performed, and the mixture was heated at 80 C. for 4 days. Dichloromethane (20 ml) was added and the mixture was filtered through celite. The solution was evaporated to dryness and the white solid obtained was solubilized in a minimum of dichloromethane. The product was precipitated with diethyl ether (80 ml), filtered, rinsed with ether and the cake was dried in vacuo. 4.62 g of white product was obtained (yield: 81%). .sup.1H NMR (DMSO-d6, ppm): 9.87 (s, 8H), 8.21 (s, 8H), 8.12 (s, 8H), 7.61 (t, 8H), 7.42 (d, 16H), 7.02 (s, 40H), 6.52 (s, 16H), 4.56 (s, 16H), 4.42 (s, 16H), 3.79 to 3.87 (m, 32H), 2.19 (quintet, 16H), 2.07 (s, 16H), 1.71 (s, 16H), 1.08 (s, 96H). m/z (ESI, positive mode): 1071.29 [M3Br].sup.3+/3 (calc=1071.03), 1455.03 [M3Br].sup.3+/3 (calc=1454.68).

Example 4: Preparation of the Salen Ligands

Intermediate 14

[0289] Calixarene 3 (10 g, 4.13 mmol) and sodium azide NaN.sub.3 (6.8 g, 103 mmol) were introduced in a reactor. The mixture was dried under vacuum for 30 min and anhydrous DMF (50 ml) was added under argon, and three vacuum/argon cycles were applied to inert the medium. The solution was stirred at 65 C. for 30 h and allowed to cool to room temperature. A saturated NaCl solution was added to precipitate the product which was then filtered. The white solid obtained was washed several times with water, methanol and finally with pentane, dried under vacuum to give 8.8 g of a white powder (yield: 86%). .sup.1H NMR (CDCl.sub.3, ppm): 7.17 (s, 40H), 6.55 (s, 16H), 4.67 (s, 16H), 3.95 (s, 16H), 3.62 to 3.65 (m, 16H), 3.20 to 3.17 (m, 16H), 1.69 (bs, 32H). .sup.13C NMR (CDCl.sub.3, ppm): 154.7; 148.9; 137.0; 134.8; 128.3; 127.7; 127.5; 114.9; 72.9; 69.7; 51, 2; 30.2; 27.4; 25.8. m/z (ESI, positive mode): 2496.1626 [M+Na.sup.+] (calc=2496.1710).

Intermediate 15

[0290] Calixarene 14 (1.21 g, 0.49 mmol) and the alkyne A (0.894 g, 4.42 mmol) were placed in a reactor under an argon atmosphere and dichloromethane (15 ml) was added. An aqueous solution (15 ml) of copper sulphate pentahydrate CuSO.sub.4.5H.sub.2O (0.1 1 g, 0.442 mmol) and sodium ascorbate (0.167 g, 0.88 mmol) was added to the reactor. The biphasic solution was stirred at room temperature under argon for 24 h. Dichloromethane (20 ml) was added and the biphasic solution was washed with a saturated solution of sodium bicarbonate NaHCO.sub.3 (35 ml). The aqueous phase was extracted 3 times with dichloromethane (30 ml). The organic phase was dried over magnesium sulphate and evaporated. The solid obtained was solubilized in a minimum amount of dichloromethane, precipitated with ether, filtered and dried under vacuum. 5 g of a yellow solid was obtained (yield=75%). .sup.1H NMR (DMSO-d.sub.6, ppm): 11.74 (s, 8H), 9.85 (s, 8H), 8.37 (s, 8H), 7.86 (s, 8H), 7.89 (s, 8H), 7.02 (s, 40H), 6.45 (s, 16H), 4.58 (bs, 16H), 4.27 (bs, 16H), 3.85 (bs, 16H), 3.55 (bs, 16H), 1.91 (bs, 16H), 1.55 (bs, 16H), 1.30 (s, 72H). .sup.13C NMR (DMSO-d.sub.6, ppm): 197.2; 158.4; 152.9; 147.5; 144.4; 136.7; 135.7; 133.5; 129.5; 127.4; 127.0; 126.4; 126.3; 121.3; 119.6; 119.5; 113.5; 71.3; 68.0; 48.3; 33.4; 27.8; 27.7; 25.6; 25.5. m/z (MALDI, DCTB matrix): 4223.01 [M+Cs.sup.+] (calc=4222.88). Elemental analysis: C=72.7% (calc=72.3%), H=6.5% (calc=6.6%), N=8.2% (calc=7.7%), O=12.5% (calc=11.5%).

Ligand 16

[0291] In a reactor under argon was charged the ammonium monochloride of cyclohexanediamine C (0.366 g, 2.43 mmol), 3,5-di-tert-butyl-2-hydroxybenzaldehyde B (0.569 g, 2.43 mmol) and 3 A molecular sieves (1 g), followed by anhydrous methanol (20 ml). The reaction was stirred at room temperature for 4 h and then a solution of calixarene 15 (1.1 g, 0.27 mmol) in anhydrous dichloromethane (30 ml) was added under argon. Triethylamine (0.965 ml, 7.02 mmol) was added under argon and the mixture was stirred for 16 h at room temperature. The solution was filtered through celite and evaporated. The solid obtained was washed with methanol and with ethanol. The yellow solid was dissolved in a minimum of diethyl ether and precipitated with ethanol. The solid was filtered and dried under vacuum to give 1.4 g of a yellow solid (yield: 79%). .sup.1H NMR (CDCl.sub.3, ppm): 14.12 (s, 8H), 13.58 (s, 8H), 8.28 (s, 8H), 8.19 (s, 8H), 7.68 (s, 8H), 7.61 (s, 8H), 7.43 (s, 8H), 7.03 to 6.95 (m, 40H), 6.46 (s, 16H), 4.55 (bs, 16H), 4.13 (bs, 16H), 3.86 (bs, 16H), 3.54 (bs, 16H), 3.24 (bs, 16H), 1.79-1.88 (m, 48H), 1.79 (m, 48H, 1.38 (s, 72H), 1.36 (s, 72H), 1.20 (s, 72H).sup.13C NMR (CDCl.sub.3, ppm): 166.0; 165.3; 160.7; 158.0; 154.9; 149.0; 147.6; 140.1; 137, 9; 136.9; 136.5; 134.9; 128.4; 127.8; 127.6; 127.1; 127.0; 126.1; 120.7; 119.0; 118 8; 117.9, 115.2; 72.9; 72.6; 71.9; 69.9; 50.1; 35.1; 35.0; 34.13; 33.2; 33.1; 31.5; 30.3; 29.5; 29.4; 27.3; 24.3 m/z (MALDI, DCTB matrix.): 6724 [m+Cs.sup.+] (calc=6721) Elemental analysis: C=75.7% (calc=74.5%), H=7.9% (calc=7.9%), N=8.3% (calc=8.5%), O=7.9% (calc=7.7%). [a].sub.D.sup.20=+105.34 (c=0.002 M in CHCl.sub.3).

Example 5: Preparation of the Catalysts

Preparation of Rhodium Catalyst 7

[0292] Calixarene 3 (3.28 g, 0.9 mmol) and chloro(1,5-cyclooctadiene)rhodium(I) dimer (1.87 g, 3.8 mmol) were introduced in a reactor and dried in vacuo. Under argon was added 30 ml of anhydrous dichloromethane and the reaction medium was placed for 2 hours at room temperature. The mixture was filtered on filter paper and dichloromethane was evaporated. The residue was dissolved in a minimum amount of dichloromethane and precipitated with diethyl ether. 4.05 g of a yellow-orange powder was obtained (yield: 80%). .sup.1H NMR (CD.sub.2Cl.sub.2, ppm): 7.64 (m, 4H), 7.32 (m, 48H), 7.01 (s, 40), 6.56 (s, 16H), 5, 41 (s, 16H), 4.48 (s, 16H), 3.97 (s, 16H), 3.79 (s, 16H), 3.05 (s, 16H), 1.66-2.5 (m, 14H). .sup.31P NMR (CD.sub.2Cl.sub.2, ppm): 26.26 (d, J.sub.P-Rh=148.9 Hz). Elemental analysis: C=62.38% (calc=62.36%), H=5.47% (calc=5.71%).

Preparation of Palladium Catalyst 8

[0293] Calixarene 5 (3 g, 0.79 mmol), potassium carbonate (3 g, 21.7 mmol, dried under vacuum with heat for 30 min) and palladium chloride (1.5 g, 8.5 mmol) were introduced in a reactor. The mixture was dried under vacuum for 30 min and then 25 ml of 3-chloropyridine was added under argon. 3 vacuum/argon cycles were performed, and the mixture was heated with stirring at 100 C. for 48 h. The solution was diluted with 60 ml of dichloromethane and was centrifuged, the solid byproducts were separated by filtration and the dichloromethane and a portion of the chloropyridine were evaporated. Then, the complex was precipitated with diethyl ether. A white-brown solid was obtained, which was filtered and washed with diethyl ether. After drying in vacuo 3.61 g of product was obtained (yield: 78%). .sup.1H NMR (DMSO, ppm): 8.63 (s, 8H), 8.56 (d, 8H), 7.97 (d, 8H), 7.49 (s, 8H), 7.33 (s, 16H), 7.25 (s, 8H), 7.01 (s, 8H), 6.97 (s, 40H). Elemental analysis: C=55.2% (calc=56.5%), H=4.6% (calc=4.6%), N=5.6% (calc=5.7%).

Preparation of Palladium Catalyst 8

[0294] Calixarene 5 (0.5 g, 0.13 mmol), potassium carbonate (0.72 g, 5.2 mmol, dried under heat and vacuum for 30 min), potassium iodide (0.863 g, 5.2 mmol, dried under heat and vacuum for 30 min) and palladium iodide (0.443 g, 1.23 mmol). Drying was performed for 30 min under vacuum and 5 ml of pyridine was added under argon. 3 vacuum/argon cycles were performed, and the mixture was heated with stirring at 100 C. for 48 h. The solution was diluted with 20 ml of dichloromethane and centrifuged. The solid byproducts were separated by filtration and the dichloromethane and pyridine was evaporated. The product was dissolved in a minimum amount of dichloromethane, and the complex was precipitated with diethyl ether, filtered and rinsed with diethyl ether. After drying under vacuum, 0.655 g of a yellow solid was obtained (yield: 71%). .sup.1H NMR (DMSO-d.sub.6, ppm): 8.46 (d, J=4.3 Hz, 16H), 7.72 (m, 8H), 7.47 (s, 8H), 7.27 (s, 8H), 7.20-7.23 (m, 24H), 6.97 to 7.03 (m, 56H), (s, 40H), 6.54 (bs, 16H), 4.57 (bs, 32H), 3.98 (bs, 16H), 3.86 (bs, 16H), 2.28 (s, 24H), 2.19 (s, 48H), 1.79 (s, 16H). Elemental analysis: C=46.89% (calc=47.13%), H=4.03% (calc=4.18%) N=4.63% (calc=4.71%).

Preparation of Palladium Catalyst 8

[0295] Calixarene 5 (0.5 g, 0.13 mmol), potassium carbonate (0.72 g, 5.2 mmol, dried under heat and for 30 min), potassium bromide (0.619 g, 5.2 mmol, dried under heat and vacuum for 30 min) and palladium bromide (0.33 g, 1.23 mmol) were introduced in a reactor. Drying was performed for 30 min under vacuum and 5 ml of pyridine was added under argon. 3 vacuum/argon cycles were performed, and the mixture was heated with stirring at 100 C. for 48 h. The solution was diluted with 20 ml of dichloromethane and centrifuged. The solid byproducts were separated by filtration the dichloromethane and pyridine were evaporated. The product was dissolved in a minimum amount of dichloromethane, and the complex was precipitated with diethyl ether, filtered and rinsed with diethyl ether. After drying in vacuo 0.431 g of a yellow solid was obtained (yield: 52%). .sup.1H NMR (DMSO-d.sub.6, ppm): 8.51 (s, 16H), 7.77 (s, 8H), 6.98 to 7.24 (m, 88H), 6.53 (s, 16H), 4.63 (bs, 32H), 3.92 (bs, 32H), 2.28 (s, 24H), 2.13 (s, 48H), 1.91 (s, 16H).

Preparation of Palladium Catalyst 9

[0296] Calixarene 6 (0.3 g, 6.5.10.sup.2 mmol), potassium carbonate (0.36 g, 2.6 mmol, dried under heat and vacuum for 30 min) and palladium bromide (0.15 g, 0.55 mmol) were introduced in a reactor. Drying was performed for 30 min under vacuum and 5 ml of pyridine was added under argon. 3 vacuum/argon cycles were performed, and the mixture was heated with stirring at 100 C. for 48 h. The solution was diluted with 20 ml of dichloromethane and centrifuged. The solid byproducts were separated by filtration the dichloromethane and pyridine were evaporated. The product was dissolved in a minimum amount of dichloromethane, and the complex was precipitated with diethyl ether, filtered and rinsed with diethyl ether. After drying in vacuo 0.35 g of a yellow solid was obtained (yield: 79%). .sup.1H NMR (DMSO-d.sub.6, ppm): 8.51 (s, 32H), 7.76 (s, 8H), 7.47 (s, 24H), 7.28-7.32 (m, 40H), 7.04 (s, 40H), 6.54 (s, 16H), 4.57 to 4.66 (m, 32H), 3.93 (s, 32H), 2.83 (s, 16H), 2.34 (s, 16H), 1.84 (s, 16H), 1.24 (s, 48H), 0.91 (s, 48H). Elemental analysis: C=54.46% (calc=54.27%), H=4.78% (calc=5.00%) N=5.19% (calc=5.27%).

Preparation of the Palladium Catalyst 13

[0297] Potassium carbonate (586 mg, 4.24 mmol) was introduced in a reactor and dried with heating under vacuum. Palladium chloride (261 mg, 1.47 mmol), calixarene 12 (500 mg, 0.14 mmol) and 3-chloropyridine (3 ml) were added at room temperature. Three vacuum-argon cycles were carried out and the mixture was heated for 36 h at 100 C. The medium was diluted with dichloromethane (10 ml), centrifuged and filtered. The solvents were evaporated, and the product was dissolved in a minimum of dichloromethane. The product was precipitated with diethyl ether/pentane and filtered. After drying, 469 mg of product was obtained (60% yield). .sup.1H NMR (DMSO-d.sub.6, ppm): 8.65 (s, 8H), 8.57 (s, 8H), 8.01 (s, 8H), 7.54 (s, 8H), 7.40 (s, 8H), 7.31 (s, 8H), 6.97 (s, 16H), 6.91 (s, 16H), 4.68 (s, 16H), 4.00 (s, 16H), 3.80 (s, 16H), 2.28 (s, 40H), 2.08 (s, 48H), 1.81 (s, 16H), 0.96 (s, 72H). Elemental analysis: C=55.54% (calc=55.43%) H=5.70% (calc=5.52%) N=5.65% (calc=6.06%).

Preparation of the Cobalt Catalyst 17

[0298] In a reactor under argon, were introduced calixarene 16 (0.5 g, 0.075 mmol) and dichloromethane (10 ml) and the mixture was stirred until completely dissolved. A solution of Co(OAc).sub.2.3H.sub.2O (0.187 g, 0.75 mmol) in anhydrous methanol (6 ml) was added to the solution of calixarene 16 under argon. The reaction was allowed to stir for 4 h at room temperature. The mixture was cooled to 0 C. followed by addition of para-toluenesulfonic acid (0.143 g, 0.75 mmol) and additional 5 ml of dichloromethane was added. The reaction was placed under 1 atm of pure oxygen and stirred at room temperature for 16 h. The solution was evaporated and the solid was washed several times with methanol and dried under vacuum. A green solid was obtained 0.534 g (yield=84%). .sup.1H NMR (DMSO-d.sub.6, ppm): 8.37 (s, 8H); 8.03 (s, 8H); 7.91 (s, 8H); 7.81-7.83 (m, 16H); 7.46-7.48 (m, 32H); 7.03-7.08 (m, 56H); 6.54 (bs, 16H); 4.64 (bs, 16H); 4.51 (bs, 16H); 3.92 (bs, 8H); 3.61 (s, 24H); 3.05 (s, 16H); 2.25 (s, 24H); 1.89-1.94 (m, 48H), 1.73-1.74 (m, 144H), 1.46-1.56 (m, 48H), 1.30 (s, 72H). .sup.13C NMR (DMSO-D.sub.6, ppm): 165.2; 164.7; 164.6; 162.2; 154.4; 147.0; 146.4; 143.4; 142.1; 137.9; 137.2; 136.5; 130.8; 129.7; 129.4; 129.0; 128.4; 127.8; 125.9; 119.7; 119.0; 117.6; 69.8; 69.4; 49.7; 49.0; 36.2; 36.1; 34.0; 31, 9; 30.8; 30.6; 29.8; 27.2; 24.7; 21:1. Elemental analysis calculated for calixarene 17+5CH.sub.2Cl.sub.2:C=64.3% (calc=64.8%), H=6.5% (calc=6.5%), N=6.6% (calc=6.3%), S=2.3% (calc=2.9%). [a].sub.D.sup.2=+1020.4 (c=8.10.sup.5 M in DMF).

Example 6: Use of the Palladium Catalysts for the Suzuki Coupling Reaction

Example 6.1: Coupling Between Bromotoluene and Phenylboronic Acid

[0299] ##STR00057##

[0300] Standard Protocol:

[0301] Catalyst 8 (7.4 mg, 1.10.sup.5 mol, 1 mol %), phenylboronic acid (182.9 mg, 1.5.10.sup.3 mol, 1.5 eq) and potassium phosphate tribasic (424.5 mg, 2.10.sup.3 mol, 2 eq) wre introduced in a reactor. The mixture was dried under vacuum for 10 min and bromotoluene (171 mg, 1.10.sup.3 mol, 1 eq) was added. The medium is placed under argon and anhydrous ethanol (2 ml) was added. 3 vacuum/argon cycles were carried out and the mixture heated with stirring at 40 C. for 2 h. The reaction was monitored by gas chromatography. When coupling dihalogenated substrates, the number of equivalents of boronic acid and base was modified/In the case of 1,2-dibromobenzene: 3 eq of base and boronic acid; in the case of 1,9-dibromoanthracene and 1,2-dichlobenzene: 3 eq of base, 2.5 eq of boronic acid.

[0302] The results of the Suzuki coupling with the catalysts 8 and 9, with respect to the temperature and loading of the catalyst are presented in Tables 1 and 1.

[0303] The results of the Suzuki coupling with the catalysts 8 and 9, with respect to the solvent, are presented in Table 2.

[0304] The results of the Suzuki coupling with the catalysts 8 and 9, with respect to the base are shown in Table 3.

[0305] The results of the Suzuki coupling, with respect to the catalyst are presented in Tables 4 and 4.

[0306] The results of the Suzuki coupling reactions, with respect to the concentration of reagents, are presented in Table 5.

TABLE-US-00002 TABLE 1 Temperature and catalyst loading. K.sub.3PO.sub.4, 0.5M in bromotoluene, 1 5 eq in boronic acid, ethanol, 2 h. T ( C.) Pd (mol %) Catalyst Conversion (%) Yield (%) 27 0.1 8 98 90 9 91 (95/6 h) 86 0.05 8 92 (99/22 h) 81 0.01 8 70 (93/22).sup. 40 0.05 8 97 85 9 93 (97/23 h) 84 0.01 8 91 (96/23 h) 87 9 89 (95/23 h) 82 0.005 8 81 (92/23 h) 80 0.005 8 92 84 9 97 91 0.001 8 93 71 9 91 72

TABLE-US-00003 TABLE 1 temperature and catalyst loading. K.sub.3PO.sub.4, 0.25M in bromotoluene, isopropanol, catalyst 8, 23 h. T ( C.) Pd (mol %) Conversion (%) 27 0.5 93 40 2 100 0.5 100 0.1 100 0.05 100 0.01 95 80 0.01 96 0.005 98 0.0025 74

TABLE-US-00004 TABLE 2 Nature of the solvent. K.sub.3PO.sub.4 0.25M in bromotoluene, Pd = 0.5 mol %, 27 C., 2 h. Conversion Conversion Solvant catalyst 8 (%) catalyst 9 (%) MeOH 71 (76/6 h) 73 (81/6 h) EtOH 98 99 EtOH anh 99 EtOHH.sub.2O 7/1 92 (99/6 h) iPrOH 74 (99/22 h) 53 (91/22 h) PrOH 97 (99/4 h) 95 (99/6 h) t-BuOH 6 (84/22 h) 2 (66/22 h) BuOH 94 (100/6 h) 95 (99/6 h) Acetonitrile 0 0 DMF 0 0 DMFH.sub.2O 7/1 67 (99/23 h) THF 0 0 THFH.sub.2O 7/1 10 (17/6 h) Toluene 22 (32/23 h) 12 (26/23 h) Toluene-H.sub.2O 7/1 72 (90/22 h)

TABLE-US-00005 TABLE 3 Nature of the base. Bromotoluene 0.25M in ethanol, Pd = 0.5 mol %, 27 C. Conversion (%) Catalyst Base t = 2 h t = 23 h 8 K.sub.3PO.sub.4 98 K.sub.2CO.sub.3 67 92 AcONa 15 29 KOH 53 64 9 K.sub.3PO.sub.4 99 K.sub.2CO.sub.3 59 95 Bu.sub.4N.sup.+OH.sup. 3 64 AcONa 14 26 KOH 53 60

TABLE-US-00006 TABLE 4 Nature of the catalyst. Conditions 1: K.sub.3PO.sub.4, 0.5M in bromotoluene, ethanol, Pd = 0.005 mol %, 80 C., 2 h. Conditions 2: K.sub.3PO.sub.4 0.25M in bromotoluene, ethanol, Pd = 0.5 mol %, 27 C., 2 h. Conditions 1, Conditions 2, Catalyst conversion (%) conversion (%) 8 92 98 .sub.8 40 9 97 99 13 85 98

TABLE-US-00007 TABLE 4 Nature of the catalyst. K.sub.3PO.sub.4, 0.25M in bromotoluene, isopropanol, Pd = 0.5 mol %, temperature, 23 h. Catalyst T ( C.) Pd (mol %) Conversion (%) 8 27 0.5 99 9 27 0.5 91 8 40 0.1 100 13 40 0.1 88

TABLE-US-00008 TABLE 5 Concentration of the mixture. K.sub.3PO.sub.4, ethanol, Pd = 0.5 mol %, catalyst 8, 27 C., 2 h. C.sub.Substrate (M) Conversion (%) 0.125 93 (98/23 h) 0.25 98 0.5 99

Example 6.2: Suzuki Coupling Between Various Brominated Substrates and Various Boronic Acids

[0307] ##STR00058##

[0308] The results are presented in Table 6 below.

TABLE-US-00009 TABLE 6 Conversion, selectivity and yield of the Suzuki coupling reaction between various brominated substrates and boronic acids. K.sub.3PO.sub.4, ethanol, 2 h. Iso- Pd lated Halogen Boronic acid T (mol C.sub.Substrate Conversion Selectivite yield Ar.sub.1Br (HO).sub.2BAr.sub.2 ( C.) %) Cata. (M) (%) (%) (%) [00059] [00060] 27 0.05 0.01 8 8 9 0.25 0.25 0.25 100 74 (100/5 h) 37 (100/23 h) [00061] [00062] 40 27 40 0.01 0.05 0.01 8 8 8 0.25 0.5 0.5 100 90 (100/4 h) 81 (98/23 h) 100 100 (100) 100 [00063] [00064] 80 0.01 8 9 0.5 0.5 100 100 100 99 [00065] [00066] 80 0.1 8 0.5 100 [00067] [00068] 80 0.05 8 0.5 97 96 [00069] [00070] 80 1 8 9 0.5 0.5 94 98 97 98 [00071] [00072] 80 1 8 9 0.5 0.5 99 100 100 100 [00073] [00074] 80 0.5 9 0.5 90 100 [00075] [00076] 80 2 8 9 0.5 0.5 89 95 85 91 [00077] [00078] 80 2 8 0.5 100 99 [00079] [00080] 80 0.5 9 0.5 100 77 [00081] [00082] 80 2 8 9 0.5 0.5 98 100 88 100 [00083] [00084] 80 0.5 9 0.5 100 100 [00085] [00086] 80 0.05 8 0.5 100 100 [00087] [00088] 80 2 9 0.5 100 98 [00089] [00090] 80 2 9 0.5 60 51 [00091] [00092] 80 2 8 9 0.5 0.5 51 74 89 89 [00093] [00094] 80 1 9 0.5 100 95 95 [00095] [00096] 80 2 9 0.5 73 [00097] [00098] 80 0.01 8 0.5 98 100 [00099] [00100] 80 0.05 8 0.5 100 [00101] [00102] 80 0.01 9 0.25 97 94 [00103] [00104] 80 0.2 8 9 0.25 99 17 95 [00105] [00106] 80 0.5 8 0.5 98 99 [00107] [00108] 80 2 8 0.5 97 98 [00109] [00110] 80 0.5 8 0.5 100 85 [00111] [00112] 80 0.1 8 0.5 100 95 95 [00113] [00114] 80 1 8 0.5 19 (90/96 h) 91 (98)

Example 6.3: Suzuki Coupling Between Various Chlorinated Substrates and Phenylboronic Acid

[0309] ##STR00115##

[0310] The results are presented in Table 7 below.

TABLE-US-00010 TABLE 7 Conversion and selectivity of the Suzuki coupling reaction between various chlorinated substrates and phenylboronic acid. K.sub.3PO.sub.4, solvent, temperature, 2 h. C.sub.Substrate T Pd (1 eq) Conversion Selectivity Halogen ( C.) (mol %) Cat. Base Solvent (M) (%) (%) [00116] 80 100 2 2 8 9 8 K.sub.3PO.sub.4 K.sub.3PO.sub.4 K.sub.3PO.sub.4 Cs.sub.2CO.sub.3 Cs.sub.2CO.sub.3 EtOH EtOH BuOH DMF/H.sub.2O 70/30 NMP/H.sub.2O 70/30 0.5 0.5 0.5 0.25 0.25 57 43 44 70 (93/23 h) 49 (76/24 h) 74 83 [00117] 100 0.5 8 K.sub.3PO.sub.4 BuOH 0.5 99 [00118] 100 1 8 K.sub.3PO.sub.4 BuOH 0.5 54 [00119] 100 1 8 K.sub.3PO.sub.4 BuOH 0.25 23 [00120] 80 2 1 9 9 K.sub.3PO.sub.4 K.sub.3PO.sub.4 EtOH EtOH 0.5 0.5 63 50 68 M, 32 D 77 M, 24 D [00121] 80 2 8 K.sub.3PO.sub.4 EtOH 0.5 47 95

Example 6.4: Studies on the Residual Palladium Content in the Products Obtained from the Suzuki Coupling

[0311] All glassware used was subsequently washed with nitric acid and rinsed with ultrapure water. Suzuki couplings were performed according to the protocol presented in Example 6.1, starting from 1 mmol. After 2 h of reaction, the reaction medium was cooled and left for 30 min at room temperature without stirring. The medium was then filtered on grade 5 filter paper and the cake was rinsed with ethanol. The filtrate was condensed under vacuum and diethyl ether or ethyl acetate (10 ml) was added followed by water. The aqueous phase was then extracted with 310 ml of diethyl ether or ethyl acetate. After combining, drying and condensing under vacuum of the organic phases, the product was evaporated under vacuum at 200 C. for one hour. The residue was mineralized in a flask fitted with a reflux condenser by adding 4 ml of concentrated nitric acid which was brought at reflux with stirring for 1 hour until a clear and homogeneous solution was obtained. The solution was then analyzed by ICP-MS. A metal content, expressed in milligrams of palladium per kilogram of product derived from the Suzuki coupling, was obtained.

[0312] The results obtained as a function of the catalyst loading are presented in Tables 8 and 8:

TABLE-US-00011 TABLE 8 Residual palladium content in the products obtained from the Suzuki coupling. K.sub.3PO.sub.4 0.5 M substrate, ethanol, 80 C., 2 h. Palladium non- Substrate Boronic acid Pd Conversion [Pd].sub.Product leached Ar.sub.1Br (HO).sub.2BAr.sub.2 (mol %) Catalyst (%) (ppm) (%) [00122] [00123] 0.5 8 9 13 100 100 100 10.6 50.8 161.6 99.7 98.6 95.4 [00124] [00125] 0.5 8 100 66.3 98.1 [00126] [00127] 2 8 100 78.7 99.4 [00128] [00129] 0.05 8 100 13.4 97.2 [00130] [00131] 1 9 100 31.5 99.6

TABLE-US-00012 TABLE 8 Residual palladium content in the products obtained from the Suzuki coupling. K.sub.3PO.sub.4, 0.25M bromotoluene, 1.5 eq phenylboronic acid, imidazoleanol, catalyst 8, 40 C., 23 h. Pd (mol %) ppm (mg .Math. kg.sup.1) 1 10.8 0.5 7.2 0.1 7.9 0.05 4.4

Example 7: Other Uses of the Metal Complexes

Example 7.1: Use of the Rhodium Catalyst in a Hydrogenation Reaction

[0313] ##STR00132##

[0314] Standard Protocol:

[0315] Calixarene 7 (3.36 mg, 5.5.10.sup.7 mol, 0.3 mol %), benzylideneacetone (214.3 mg, 1.467.10.sup.3 mol) and isopropanol (10 ml) were introduced in an autoclave. The reactor was placed under dihydrogen atmosphere by performing two compression (10 bar)/decompression cycles and injecting 30 bars. The medium was stirred at room temperature and its composition was analyzed with gas chromatography coupled to electrospray mass spectrometry. The results are shown in the Table 9 below.

TABLE-US-00013 TABLE 9 Use of the rhodium catalyst 7 for the hydrogenation reaction. Solvent: isopropanol Catalyst loading T t Conversion [00133] [00134] [00135] [00136] 1% 100 C. 2 h 100% 88.6% 11.4% 0.05% 100 C. 2 h 60% 3.7% 3% 52.6% 1.5% TA 22 h 100% 1.2% 2.3% 96.5% 0.3% TA 22 h 72 h 18% 100% 5.6% 2.5% 92.1%

Example 7.2: Use of the Palladium Catalysts in the Heck Coupling

[0316] ##STR00137##

[0317] Standard Protocol:

[0318] Catalyst 8 (7.4 mg, 1.25.10.sup.3, mmol) and potassium phosphate tribasic (424 mg, 2 mmol) were introduced in a reactor and dried under vacuum for 10 min. Bromobenzene (105 l, 1 mmol), butyl acrylate (213 l, 1.5 mmol) and anhydrous dimethylformamide (4 ml) were added under an argon atmosphere. 3 vacuum/argon cycles were performed, and the mixture was stirred at 100 C. for 18 h, giving 57% conversion.

[0319] The results are presented in the following table 10:

TABLE-US-00014 TABLE 10 Conversions obtained in the Heck coupling. K.sub.3PO.sub.4, 0.25 M of butyl acrylate, 2 h. T Pd Conversion Substrate ( C.) (mol %) Catalyst Solvent (%) [00138] 100 130 1 1 2 8 9 8 9 8 DMF DMF NMP DMF DMF DMF 57 (18 H) 6 (13/18 h) 62 (22 h) 62 (22 h) 86 (24 h) 56 (18 h) [00139] 80 100 1 1 9 8 9 DMF DMF DMF 92 (100/4 h) 100 100

Example 7.3: Epoxide Opening Reaction

[0320] i. Opening of Epibromohydrin

##STR00140##

[0321] Catalyst 17 (32 mg, 0.034 mmol, 2 mol %), epibromohydrin (0.141 ml. 1.7 mmol), chlorobenzene (0.05 ml, 0.5 mmol) and 0.197 ml of THF were introduced in a reactor. Water (0.044 ml, 2.5 mmol) was added with stirring. The reaction was allowed to stir for 24 h at room temperature and 5 ml of dichloromethane, Amberlyst 15 (16 mg) and 2.2-dimethoxypropane (0.418 ml, 3.4 mmol) were added. Stirring was continued for 18 h at room temperature. The reaction was monitored by gas chromatography: the use of an achiral column provides access to the conversion and that of a chiral column to the enantiomeric excess (ee). After a first catalytic reaction, the catalyst 17 was precipitated with diethyl ether, filtered and reengaged in a new catalytic reaction with a new batch of products and solvents. The catalyst 17 was thus evaluated through three catalytic cycles.

[0322] The results are presented in Table 11 below.

TABLE-US-00015 TABLE 11 Conversion and enantiomeric excesses obtained in the epoxide opening reaction [00141] Catalyst loading Conversion e.e. (mol %) (%) (%) Cycle 1 2 100 94 Cycle 2 2 100 94 Cycle 3 2 43 94

[0323] Catalyst 17 (17 mg, 0.020 mmol, 2 mol %), cyclohexene oxide (0.100 ml. 0.99 mmol), chlorobenzene (0.025 ml. 0.25 mmol) and 0.210 ml of toluene were introduced in a reactor. Water (0.021 ml, 1.18 mmol) was added with stirring. The reaction was allowed to stir for 6 days at room temperature. The reaction was monitored by gas chromatography: using an achiral column provides access to the conversion and using a chiral column to enantiomeric excess. 100% conversion was obtained after 6 days, with an enantiomeric excess of 76%.

Example 7.4: Residual Content of Cobalt in the Product Resulting from the Opening of Epibromohydrin

[0324] At the end of the reaction, the dichloromethane solution was evaporated, and the product was extracted with ether. The suspension was filtered through filter paper and the filtrate was evaporated under reduced pressure. The residue obtained was evaporated under vacuum at 200 C. for 1 h, 4 ml of concentrated nitric acid was added which was brought to reflux with stirring for 1 h until a clear and homogeneous solution was obtained. The solution was then analyzed by ICP-MS. A metal content expressed in milligrams of cobalt per kilogram of product resulting from the opening of epibromohydrin was obtained.

[0325] The result obtained is shown in Table 12:

TABLE-US-00016 TABLE 12 Residual cobalt content in the reaction product. Substrate Co Conversion [Co].sub.Prod. Ar.sub.1Br (mol %) (%) (ppm) [00142] 1 100 1.2

Example 7.5: Residual Rhodium Content in the Products of the Hydrogenation Reaction

[0326] At the end of the reaction, the reaction medium was left for 30 min at room temperature, filtered, and a mineralization protocol and analysis identical to that described in the example 5.4 was used.

TABLE-US-00017 TABLE 13 Residual rhodium content in the hydrogenation reaction products. T t Conv. [Rh].sub.Prod. Substrate Rh (mol %) ( C.) (h) (%) (ppm) [00143] 0.3 RT 49 98.3 6.2 [00144] 0.05 100 3 100 2.4