US2004138487A1PendingUtilityA1
Synthesis of non-C2-symmetric bisphosphine ligands as catalysts for asymmetric hydrogenation
Est. expiryMar 19, 2021(expired)· nominal 20-yr term from priority
C07F 9/653C07F 15/0073B01J 31/2295B01J 31/2433B01J 31/2457B01J 2531/822C07F 9/5027B01J 31/248B01J 31/2476C07F 9/65683B01J 31/24B01J 31/2409B01J 2231/641B01J 2531/0266B01J 31/2414C07B 53/00B01J 2231/645C07F 9/5045B01J 31/2452
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Claims
Abstract
Non-C 2 -symmetric bisphospholane ligands and methods for their preparation are described. Use of metal/non-C 2 -symmetric bisphospholane complexes to catalyze asymmetric transformation reactions to provide high enantiomeric excesses of formed compounds is also described.
Claims
exact text as granted — not AI-modifiedWhat is claimed is:
1 . A non-C 2 bisphosphine ligand of the structural formula:
wherein the achiral phosphorous group includes at least one achiral phosphorous atom having at least two bonds to atoms other than the bridge;
the chiral phosphorous group comprises at least one phosphorous atom, wherein the at least one phosphorous atom is chiral or the at least one phosphorous atom is bonded to a chiral substituent; and
the Bridge is a —(CH 2 ) n — where n is an integer from 1 to 12; a 1,2-divalent phenyl; or a 1,2-divalent substituted phenyl.
2 . The ligand according to claim 1 , wherein the achiral phosphorous group is
wherein R is t-butyl, isopropyl, adamantyl, (1,1-dimethylpropane), (1,1-diethylbutane), c-C 5 H 9 , or c-C 6 H 11 .
3 . The ligand according to claim 1 , wherein the chiral phosphorous group is
wherein R is t-butyl, isopropyl, adamantyl, (1,1-dimethylpropane), (1,1-diethylbutane) c-C 5 H 9 , or c-C 6 H 11 ;
R 2 is methyl, ethyl, isopropyl, cyclohexyl, benzyl, a ring substituted benzyl, an aryl, or a ring substituted aryl; and
R 3 is OBn, OH, sulphonate, or hydrogen; or
its corresponding enantiomer.
4 . The ligand according to claim 1 which is 1-(di-tert-butyl-phosphanyl borane)-((R)-2-tert-butyl-methyl-phosphanyl borane) ethane.
5 . The ligand according to claim 1 which is 1-((S)-2,2′-phosphanyl-1,1′-binaphthyl)-2-((R)-2-tert-butyl-methyl-phosphanyl) ethane.
6 . The ligand according to claim 1 which is 1-((R)-2-tert-butyl-methyl-phosphanyl)-2-((R,R)—),5-dialkylphosphanyl) ethane.
7 . A compound of the structural formula
wherein R is t-butyl, isopropyl, adamantyl, (1,1-dimethylpropane), (1,1-diethylbutane), c-C 5 H 9 , or c-C 6 H 11 ; and Ms is mesylate.
8 . A compound of the structural formula
wherein R is t-butyl, isopropyl, adamantyl, (1,1-dimethylpropane), (1,1-diethylbutane), c-C 5 H 9 , or c-C 6 H 11 ; and Ms is mesylate.
9 . A compound of the structural formula
wherein R is t-butyl, isopropyl, adamantyl, (1,1-dimethylpropane), (1,1-diethylbutane), c-C 5 H 9 , or c-C 6 H 1 .
10 . A non-C 2 bisphosphine ligand of the structural formula:
wherein:
the achiral phosphorous group includes at least one achiral phosphorous atom having at least two bonds to atoms other than the bridge;
the chiral phosphorous group comprises at least one phosphorous atom, wherein the least one phosphorous atom is chiral or the at least one phosphorous atom is bonded to a chiral substituent; and
each Y is independently halogen, alkyl, alkoxy, aryl, aryloxy, nitro, amino, vinyl, substituted vinyl, alkynyl, or sulfonic acid and n is an integer from 0 to 4 equal to the number of unsubstituted aromatic ring carbons.
11 . The ligand according to claim 10 , wherein the achiral phosphorous group is
wherein R is t-butyl, isopropyl, adamantyl, (1,1-dimethylpropane), (1,1-diethylbutane), c-C 5 H 9 , or c-C 6 H 11 .
12 . The ligand according to claim 10 , wherein the chiral phosphorous group is
wherein R is t-butyl, isopropyl, adamantyl, (1,1-dimethylpropane), (1,1-diethylbutane), c-C 5 H 9 , or c-C 6 H 11 ;
R 2 is methyl, ethyl, isopropyl, cyclohexyl, benzyl, a ring substituted benzyl, an aryl, or a ring substituted aryl; and
R 3 is OBn, OH, sulphonate, or hydrogen; or
its corresponding enantiomer.
13 . The ligand according to claim 10 which is 1-((R)-2-tert-butyl-methyl-phosphanyl)-2-((R,R)-2,5-dialkylphosphanyl) benzene.
14 . A catalyst of the structural formula:
wherein:
the achiral phosphorous group includes at least one achiral phosphorous atom having at least two bonds to atoms other than the bridge;
the chiral phosphorous group comprises at least one phosphorous atom, wherein the at least one phosphorous atom is chiral or the at least one phosphorous atom is bonded to a chiral substituent;
a Bridge is a —(CH 2 ) n — where n is an integer from 1 to 12; a 1,2-divalent phenyl; or a 1,2-divalent substituted phenyl;
M is a transition metal, an actinide, or a lanthanide; and
Z is BF 4 , PF 6 , SbF 6 , OTf, or ClO 4 ; or
its corresponding enantiomer.
15 . The catalyst of claim 14 , wherein M is rhodium.
16 . A method for forming a ligand with the structural formula
wherein R is t-butyl, isopropyl, adamantyl, (1,1-dimethylpropane), (1,1-diethylbutane), c-C 5 H 9 , or c-C 6 H 11 ; and
R 2 is an alkyl, cyclohexyl, benzyl, or phenyl;
comprising the step of reacting a compound of the formula
wherein R 2 is an alkyl, benzyl, or phenyl, in the presence of s-BuLi and THF with a second compound of the formula
wherein R is t-butyl, isopropyl, adamantyl, (1,1-dimethylpropane), (1,1-diethylbutane), c-C 5 H 9 , or c-C 6 H 11 ; and Ms is mesylate.
17 . A method for forming a ligand with the structural formula
wherein R is t-butyl, isopropyl, adamantyl, (1,1-dimethylpropane), (1,1-diethylbutane), c-C 5 H 9 , or c-C 6 H 11 ; and
R 9 is an alkyl or benzyl;
comprising the step of reacting a compound of the formula
wherein R is t-butyl, isopropyl, adamantyl, (1,1-dimethylpropane), (1,1-diethylbutane), c-C 5 H 9 , or c-C 6 H 11 , in the presence of n-BuLi and THF, with a second compound selection from the group consisting of
wherein R 2 is an alkyl or cyclohexyl; and Ms is mesylate.
18 . A method for forming a ligand with the structural formula
wherein R is t-butyl, isopropyl, adamantyl, (1,1-dimethylpropane), (1,1-diethylbutane), c-C 5 H 9 , or c-C 6 H 11 ;
comprising the step of reacting a compound of the formula
wherein R is t-butyl, isopropyl, adamantyl, (1,1-dimethylpropane), (1,1-diethylbutane), c-C 5 H 9 , or c-C 6 H 11 , in the presence of n-BuLi and THF, with a second compound of the formula
19 . A method for forming a ligand with the structural formula
wherein R is t-butyl, isopropyl, adamantyl, (1,1-dimethylpropane), (1,1-diethylbutane), c-C 5 H 9 , or C—C 6 HI 1; and
R 2 is an alkyl or benzyl;
comprising the step of reacting a compound of the formula
wherein R 2 is an alkyl or benzyl, in the presence of s-BuLi and THF with a second compound of the formula
wherein R is t-butyl, isopropyl, adamantyl, (1,1-dimethylpropane), (1,1-diethylbutane), c-C 5 H 9 , or c-C 6 H 11 .
20 . A method for forming a ligand with the structural formula
wherein R is t-butyl, isopropyl, adamantyl, (1,1-dimethylpropane), (1,1-diethylbutane), c-C 5 H 9 , or c-C 6 H 11 ; and
R 2 is an alkyl or benzyl;
comprising the step of reacting a compound of the formula
wherein R 2 is an alkyl or benzyl, in the presence of s-BuLi and THF with a second compound of the formula
wherein R is t-butyl, isopropyl, adamantyl, (1,1-dimethylpropane), (1,1-diethylbutane), c-C 5 H 9 , or c-C 6 H 11 .
21 . A method for forming a ligand with the structural formula
wherein R is t-butyl, isopropyl, adamantyl, (1,1-dimethylpropane), (1,1-diethylbutane), C—C 5 H 9 , or C—C 6 H 11 ;
comprising the step of reacting a compound of the formula
in the presence of s-BuLi and THF with a second compound of the formula
wherein R is t-butyl, isopropyl, adamantyl, (1,1-dimethylpropane), (1,1-diethylbutane), c-C 5 H 9 , or c-C 6 H 11 .
22 . A method for forming a ligand with the structural formula
or its corresponding enantiomer, wherein R is t-butyl, isopropyl, adamantyl, (1,1-dimethylpropane), (1,1-diethylbutane), c-C 5 H 9 , or c-C 6 H 11 , and Ms is mesylate, comprising the steps of:
(a) reacting a compound of the formula
wherein R is t-butyl, isopropyl, adamantyl, (1,1-dimethylpropane), (1,1-diethylbutane), c-C 5 H 9 , or c-C 6 H 11 , in the presence of K 2 CO 3 and DMSO with a second compound of the formula
or its corresponding enantiomer, wherein R′ is methyl, benzyl, aryl, or isopropyl and R″ is hydrogen, methyl, benzyl, aryl, or isopropyl, forming a first intermediate having the structural formula
or its corresponding enantiomer, wherein R is t-butyl, isopropyl, adamantyl, (1,1-dimethylpropane), (1,1-diethylbutane), c-C 5 H 9 , or c-C 6 H 11 ;
(b) reacting the frist intermediate with NaBH 4 and water in the presence of THF, forming a second intermediate of the formula
wherein R is t-butyl, isopropyl, adamantyl, (1,1-dimethylpropane), (1,1-diethylbutane), c-C 5 H 9 , or c-C 6 H 11 ; and
(c) reacting the second intermediate in the presence of pyridine with MsCl.
23 . A method for forming a ligand with the structural formula
or its corresponding enantiomer, wherein R is t-butyl, isopropyl, adamantyl, (1,1-dimethylpropane), (1,1-diethylbutane), c-C 5 H 9 , or c-C 6 H 11 ;
comprising the step of reacting a compound of the formula
wherein R is t-butyl, isopropyl, adamantyl, (1,1-dimethylpropane), (1,1-diethylbutane), c-C 5 H 9 , or c-C 6 H 11 and Ms is mesylate in the presence of n-BuLi with a second compound of the formula
wherein R is t-butyl, isopropyl, adamantyl, (1,1-dimethylpropane), (1,1-diethylbutane), c-C 5 H 9 , or c-C 6 H 11 .
24 . A method for forming a ligand with the structural formula
comprising the step of reacting a compound of the formula
wherein R is t-butyl and Ms is mesylate, in the presence of n-BuLi with a second compound of the formula
25 . A method for forming a chiral ligand of the structural formula or the corresponding enantiomer
wherein R is t-butyl, isopropyl, adamantyl, (1,1-dimethylpropane), (1,1-diethylbutane), c-C 5 H 9 , or c-C 6 H 1 ; and R 1 is alkyl;
comprising the steps of
(a) reacting 1,2-dibromobenzene in the presence of tetra-triphenyl phosphene palladium and triethyl-amine with phosphonic acid diethyl ester forming (2-bromo-phenyl)-phosphonic acid diethyl ester;
(b) reacting (2-bromo-phenyl)-phosphonic acid diethyl ester with lithium aluminum hydride forming 2-bromo-phenyl-phosphane;
(c) reacting 2-bromo-phenyl-phosphane in the presence of n-BuLi with a compound of the structural formula
wherein R 1 is alkyl to form an intermediate having the structural formula
wherein R 1 is alkyl; and
(d) reacting the intermediate in the presence of t-BuLi with a second compound having the structural formula
wherein R is t-butyl, isopropyl, adamantyl, (1,1-dimethylpropane), (1,1-diethylbutane), c-C 5 H 9 , or c-C 6 H 11 .
26 . A method for forming a chiral ligand of the structural formula or the corresponding enantiomer
wherein R is t-butyl, isopropyl, adamantyl, (1,1-dimethylpropane), (1,1-diethylbutane), c-C 5 H 9 , or c-C 6 H 11 ;
comprising the steps of
(a) reacting 2-bromo-phenyl-phosphane in the presence of n-BuLi with 2,2′-bis-chloromethyl-[1,1′]binaphthalenyl forming (2-bromo-phenyl)-methyl-(2′-methyl-[1,1′]binaphthalenyl-2-ylmethyl)-phosphane; and
(b) reacting (2-bromo-phenyl)-methyl-(2′-methyl-[1,1′]binaphthalenyl-2-ylmethyl)-phosphane in the presence of t-BuLi with a compound having the structural formula
wherein R is t-butyl, isopropyl, adamantyl, (1,1-dimethylpropane), (1,1-diethylbutane), c-C 5 H 9 , or c-C 6 H 11 .
27 . A method for forming a chiral ligand of the structural formula or the corresponding enantiomer
wherein R is t-butyl, isopropyl, adamantyl, (1,1-dimethylpropane), (1,1-diethylbutane), c-C 5 H 9 , or c-C 6 H 11 ; and R 1 is alkyl;
comprising the steps of
(a) reacting 2-bromo-phenyl-phosphane in the presence of n-BuLi with a compound of the structural formula
wherein R 1 is alkyl to form an intermediate having the structural formula
wherein R 1 is alkyl; and
(b) reacting the intermediate in the presence of t-BuLi with a second compound having the structural formula
wherein R is t-butyl, isopropyl, adamantyl, (1,1-dimethylpropane), (1,1-diethylbutane), c-C 5 H 9 , or c-C 6 H 11 .
28 . A method for an asymmetric transformation comprising the step of reacting a substrate with general structural formula
wherein X is N, O, or C; R 1 is an alkyl, a carboxylic acid derivative, a carboxylic ester, or a nitrile; R 2 is an alkyl, an acetyl derivative, or a carboxylic acid; R 3 is an alkyl or hydrogen; and R 4 is the R 3 alkyl or hydrogen;
with a compound of the structural formula, the corresponding enantiomer, or a solvate thereof
wherein:
the achiral phosphorous group includes at least one achiral phosphorous atom having at least two bonds to atoms other than the bridge;
the chiral phosphorous group comprises at least one phosphorous atom, wherein the at least one phosphorous atom is chiral or the at least one phosphorous atom is bonded to a chiral substituent; and
a Bridge is a —(CH 2 ) n — where n is an integer from 1 to 12; a 1,2-divalent phenyl; or a 1,2-divalent substituted phenyl;
M is a transition metal; an actinide; or a lanthanide;
or its corresponding enantiomer, or a solvate thereof.
29 . The method of claim 28 , wherein M is rhodium.
30 . The method of claim 28 , wherein the asymmetric transformation is a hydrogenation reaction.
31 . The method of claim 28 , wherein the substrate is 3-cyano-5-methylhex-3-enoic acid.
32 . The method of claim 28 , wherein a product of the asymmetric transformation has a high degree of enantiomeric excess.Cited by (0)
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