CYCLIC SUPPORTED CATALYSTS
The present invention relates to ligands based on calixarenes, metal complexes including such ligands and their use as homogeneous or heterogeneous catalysts.
1 - 17 . (canceled)
18 . Compound of general formula (I):
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 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 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):
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 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 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):
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 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 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):
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 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 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 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 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 :
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 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 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 :
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 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 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:
29 . Method of catalyzing a reaction selected from the group consisting of reduction reactions, or reduction reactions in the presence of H 2 or the hydrogenation of carbonyl, alkene, alkyne or arene, the oxidation reactions, or oxidation reactions in the presence of O 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 2 , and asymmetric catalysis reactions, or the epoxide opening reactions or asymmetric catalysis reactions allowing C—C or C—X bond formation, wherein the catalyst is a compound of formula (IC):
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 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 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):
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 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):
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 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):
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 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 2 Me, OSO 2 (C 7 H 7 ) and OSO 2 CF 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):
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 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 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,
with a metal complex of formula (L′)M n+ where M 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):
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 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 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):
in which:
V represents a leaving group, or chosen from the group consisting of halogens, or Cl, Br and I and sulfonates, or OSO 2 Me, OSO 2 (C 7 H 7 ) et OSO 2 CF 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)
in which:
G represents a grafting group of said group Q′, or a N 3 group,
and comprising a step of contacting said compound of formula (VIII) with said group Q′
to obtain a compound of formula (IB)
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),
to obtain a compound of formula (IA),
and comprising a step of contacting said compound of formula (IA),
with a metal complex of formula LM m+ ,
wherein:
M 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.