US 7,247,731 B2Granted

Ligands for metals and improved metal-catalyzed processes based thereon

AssigneeMassachusetts Institute of Technology

InventorsStephen L. Buchwald, David W. Old, John P. Wolfe, Michael Palucki, Ken Kamikawa

Life of this patent

Estimating the term…

Abstract

One aspect of the present invention relates to novel ligands for transition metals. A second aspect of the present invention relates to the use of catalysts comprising these ligands in transition metal-catalyzed carbon-heteroatom and carbon-carbon bond-forming reactions. The subject methods provide improvements in many features of the transition metal-catalyzed reactions, including the range of suitable substrates, reaction conditions, and efficiency.

Claims24

Dependent claims

A method, comprising the step of:

combining a compound represented by ArX, a compound represented by HN(R′)R″, a transition metal, a ligand, and a base, thereby forming a compound represented by ArN(R′)R″:
wherein
Ar is selected from the set consisting of optionally substituted monocyclic and polycyclic aromatic and heteroaromatic moieties;
X is selected from the set consisting of Cl, and Br;
R′ and R″ are selected, independently for each occurrence, from the set consisting of H, alkyl, heteroalkyl, aryl, heteroaryl, aralkyl, alkoxyl, amino, trialkylsilyl, and triarylsilyl;
R′ and R″, taken together, may form an optionally substituted ring consisting of 3-10 backbone atoms inclusive;
said ring optionally comprising one or more heteroatoms beyond the nitrogen to which R′ and R″ are bonded;
R′ and/or R″ may be covalently linked to Ar such that the amination reaction is intramolecular;
the transition metal is palladium;
the ligand of the present invention is selected from the group consisting of structures 1-7 inclusive:
wherein
A and B independently represent fused rings selected from the group consisting of monocyclic or polycyclic cycloalkyls, cycloalkenyls, aryls, and heterocyclic rings, said rings having 4 to 8 backbone atoms;
X and Y represent, independently for each occurrence, N, P, As, OR, or SR;
R, R1, R2, R3, and R4, for each occurrence, independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or —(CH2)m—R80;
R5 and R6, for each occurrence, independently represent halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or —(CH2)m—R80;
A and B independently are unsubstituted or substituted with R5 and R6, respectively, any number of times up to the limitations imposed by stability and the rules of valence;
R1 and R2, or R3 and R4, or both, taken together optionally represent a ring having 5-7 atoms in the backbone of said ring;
said ring having zero, one or two heteroatoms in its backbone;
and said ring is substituted or unsubstituted;
R80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl;
m is independently for each occurrence an integer in the range 0 to 8 inclusive;
and
the ligand, when chiral, is mixture of enantiomers or a single enantiomer;
wherein
X and Y represent, independently for each occurrence, N, P, As, OR, or SR;
R, R1, R2, R3, R4, R5, R6, R7, and R8, for each occurrence, independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or —(CH2)m—R80;
or two substituents, with an ortho-relationship therebetween, selected from the group consisting of R1, R2, R3, R4, R5, R6, R7, and R8, taken together, represent a ring having 5-7 atoms in the backbone of said ring;
said ring having zero, one or two heteroatoms in its backbone;
and said ring is substituted or unsubstituted;
R80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl;
m is independently for each occurrence an integer in the range 0 to 8 inclusive;
and
the ligand, when chiral, is mixture of enantiomers or a single enantiomer;
wherein
X and Y represent, independently for each occurrence, N, P, As, OR, or SR;
R, R1, R2, R3, and R4, for each occurrence, independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or —(CH2)m—R80;
or R1 and R2, or R3 and R4, or both, taken together represent a ring having 5-7 atoms in the backbone of said ring;
said ring having zero, one or two heteroatoms in its backbone;
and said ring is substituted or unsubstituted;
R5 and R6, for each occurrence, independently represent halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or —(CH2)m—R80;
the B and B′ rings of the binaphthyl core independently are unsubstituted or substituted with R5 and R6, respectively, any number of times up to the limitations imposed by stability and the rules of valence;
R80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl;
m is independently for each occurrence an integer in the range 0 to 8 inclusive;
and
the ligand, when chiral, is mixture of enantiomers or a single enantiomer;
wherein
R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and —(CH2)m—R80;
the A and A′ rings of the biphenyl core independently are unsubstituted or substituted with R1 and R2, respectively, any number of times up to the limitations imposed by stability and the rules of valence;
R1 and R2 are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, —SiR3, and —(CH2)m—R80;
R80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl;
m is independently for each occurrence an integer in the range 0 to 8 inclusive;
and
the ligand, when chiral, is mixture of enantiomers or a single enantiomer;
wherein
R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and —(CH2)m—R80;
the A, B, A′, and B′ rings of the binaphthyl core independently are unsubstituted or substituted with R1, R2, R3, and R4, respectively, any number of times up to the limitations imposed by stability and the rules of valence;
R1, R2, R3, and R4, are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, —SiR3, and —(CH2)m—R80;
R80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl;
m is independently for each occurrence an integer in the range 0 to 8 inclusive;
and
the ligand, when chiral, is mixture of enantiomers or a single enantiomer;
wherein
R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and —(CH2)m—R80;
the A and A′ rings of the biphenyl core independently are unsubstituted or substituted with R1 and R2, respectively, any number of times up to the limitations imposed by stability and the rules of valence;
R1 and R2 are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, —SiR3, and —(CH2)m—R80;
R80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl;
m is independently for each occurrence an integer in the range 0 to 8 inclusive;
and
the ligand, when chiral, is mixture of enantiomers or a single enantiomer;
wherein
R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and —(CH2)m—R80;
the A, B, A′, and B′ rings of the binaphthyl core independently are unsubstituted or substituted with R1, R2, R3, and R4, respectively, any number of times up to the limitations imposed by stability and the rules of valence;
R1, R2, R3, and R4, are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, —SiR3, and —(CH2)m—R80;
R80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl;
m is independently for each occurrence an integer in the range 0 to 8 inclusive;
and
the ligand, when chiral, is mixture of enantiomers or a single enantiomer;
and
the base is selected from the set consisting of carbonates, phosphates, fluorides, and alkoxides.

76 more elements

A method, comprising the step of:

combining a compound represented by ArX, a compound represented by Ar′B(OH)2, a transition metal, a ligand, and a base, thereby forming a compound represented by Ar—Ar′:
wherein
Ar and Ar′ are independently selected from the set consisting of optionally substituted monocyclic and polycyclic aromatic and heteroaromatic moieties;
X is selected from the set consisting of Cl, and Br;
Ar and Ar′ may be covalently linked such that the reaction is intramolecular;
the transition metal is palladium;
the ligand of the present invention is selected from the group consisting of structures 1-7 inclusive:
wherein
A and B independently represent fused rings selected from the group consisting of monocyclic or polycyclic cycloalkyls, cycloalkenyls, aryls, and heterocyclic rings, said rings having 4 to 8 backbone atoms;
X and Y represent, independently for each occurrence, N, P, As, OR, or SR;
R, R1, R2, R3, and R4, for each occurrence, independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or —(CH2)m—R80;
R5 and R6, for each occurrence, independently represent halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, arnidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or —(CH2)m—R80;
A and B independently are unsubstituted or substituted with R5 and R6, respectively, any number of times up to the limitations imposed by stability and the rules of valence;
R1 and R2, or R3 and R4, or both, taken together optionally represent a ring having 5-7 atoms in the backbone of said ring;
said ring having zero, one or two heteroatoms in its backbone;
and said ring is substituted or unsubstituted;
R80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl;
m is independently for each occurrence an integer in the range 0 to 8 inclusive;
and
the ligand, when chiral, is mixture of enantiomers or a single enantiomer;
wherein
X and Y represent, independently for each occurrence, N, P, As, OR, or SR;
R, R1, R2, R3, R4, R5, R6, R7, and R8, for each occurrence, independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or —(CH2)m—R80;
or two substituents, with an ortho-relationship therebetween, selected from the group consisting of R1, R2, R3, R4, R5, R6, R7, and R8, taken together, represent a ring having 5-7 atoms in the backbone of said ring;
said ring having zero, one or two heteroatoms in its backbone;
and said ring is substituted or unsubstituted;
R80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl;
m is independently for each occurrence an integer in the range 0 to 8 inclusive;
and
the ligand, when chiral, is mixture of enantiomers or a single enantiomer;
wherein
X and Y represent, independently for each occurrence, N, P, As, OR, or SR;
R, R1, R2, R3, and R4, for each occurrence, independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or —(CH2)m—R80;
or R1 and R2, or R3 and R4, or both, taken together represent a ring having 5-7 atoms in the backbone of said ring;
said ring having zero, one or two heteroatoms in its backbone;
and said ring is substituted or unsubstituted;
R5 and R6, for each occurrence, independently represent halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or —(CH2)m—R80;
the B and B′ rings of the binaphthyl core independently are unsubstituted or substituted with R5 and R6, respectively, any number of times up to the limitations imposed by stability and the rules of valence;
R80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl;
m is independently for each occurrence an integer in the range 0 to 8 inclusive;
and
the ligand, when chiral, is mixture of enantiomers or a single enantiomer;
wherein
R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and —(CH2)m—R80;
the A and A′ rings of the biphenyl core independently are unsubstituted or substituted with R1 and R2, respectively, any number of times up to the limitations imposed by stability and the rules of valence;
R1 and R2 are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, —SiR3, and —(CH2)m—R80;
R80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl;
m is independently for each occurrence an integer in the range 0 to 8 inclusive;
and
the ligand, when chiral, is mixture of enantiomers or a single enantiomer;
wherein
R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and —(CH2)m—R80;
the A, B, A′, and B′ rings of the binaphthyl core independently are unsubstituted or substituted with R1, R2, R3, and R4, respectively, any number of times up to the limitations imposed by stability and the rules of valence;
R1, R2, R3, and R4, are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, —SiR3, and —(CH2)m—R80;
R80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl;
m is independently for each occurrence an integer in the range 0 to 8 inclusive;
and
the ligand, when chiral, is mixture of enantiomers or a single enantiomer;
wherein
R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and —(CH2)m—R80;
the A and A′ rings of the biphenyl core independently are unsubstituted or substituted with R1 and R2, respectively, any number of times up to the limitations imposed by stability and the rules of valence;
R1 and R2 are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, —SiR3, and —(CH2)m—R80;
R80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl;
m is independently for each occurrence an integer in the range 0 to 8 inclusive;
and
the ligand, when chiral, is mixture of enantiomers or a single enantiomer;
wherein
R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and —(CH2)m—R80;
the A, B, A′, and B′ rings of the binaphthyl core independently are unsubstituted or substituted with R1, R2, R3, and R4, respectively, any number of times up to the limitations imposed by stability and the rules of valence;
R1, R2, R3, and R4, are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, —SiR3, and —(CH2)m—R80;
R80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl;
m is independently for each occurrence an integer in the range 0 to 8 inclusive;
and
the ligand, when chiral, is mixture of enantiomers or a single enantiomer;
and
the base is selected from the set consisting of carbonates, phosphates, fluorides, and alkoxides.

73 more elements

A method, comprising the step of:

combining a compound represented by ArX, a compound represented by RBR′2, a transition metal, a ligand, and a base, thereby forming a compound represented by Ar—R:
wherein
Ar is selected from the set consisting of optionally substituted monocyclic and polycyclic aromatic and heteroaromatic moieties;
R is selected from the set consisting of optionally substituted alkyl, heteroalkyl, and aralkyl;
R′ is selected, independently for each occurrence, from the set of alkyl and heteroalkyl;
the carbon-boron bond of said alkyl and heteroalkyl groups being inert under the reaction conditions, e.g., BR′2 taken together represents 9-borobicyclo[3.3.1]nonyl.
X is selected from the set consisting of Cl, and Br;
Ar and R may be covalently linked such that the reaction is intramolecular;
the transition metal is palladium;
the ligand of the present invention is selected from the group consisting of structures 1-7 inclusive:
wherein
A and B independently represent fused rings selected from the group consisting of monocyclic or polycyclic cycloalkyls, cycloalkenyls, aryls, and heterocyclic rings, said rings having 4 to 8 backbone atoms;
X and Y represent, independently for each occurrence, N, P, As, OR, or SR;
R, R1, R2, R3, and R4, for each occurrence, independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or —(CH2)m—R80;
R5 and R6, for each occurrence, independently represent halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate;
urea, thiourea, or —(CH2)m—R80;
A and B independently are unsubstituted or substituted with R5 and R6, respectively, any number of timesup to the limitations imposed by stability and the rules of valence;
R1 and R2, or R3 and R4, or both, taken together optionally represent a ring having 5-7 atoms in the backbone of said ring;
said ring having zero, one or two heteroatoms in its backbone;
and said ring is substituted or unsubstituted;
R80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl;
m is independently for each occurrence an integer in the range 0 to 8 inclusive;
and
the ligand, when chiral, is mixture of enantiomers or a single enantiomer;
wherein
X and Y represent, independently for each occurrence, N, P, As, OR, or SR;
R, R1, R2, R3, R4, R5, R6, R7, and R8, for each occurrence, independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, mime, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or —(CH2)m—R80;
or two substituents, with an ortho-relationship therebetween, selected from the group consisting of R1, R2, R3R4, R5, R6, R7, and R8, taken together, represent a ring having 5-7 atoms in the backbone of said ring;
said ring having zero, one or two heteroatoms in its backbone;
and said ring is substituted or unsubstituted;
R80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl;
m is independently for each occurrence an integer in the range 0 to 8 inclusive;
and
the ligand, when chiral, is mixture of enantiomers or a single enantiomer;
wherein
X and Y represent, independently for each occurrence, N, P, As, OR, or SR;
R, R1, R2, R3, and R4, for each occurrence, independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or —(CH2)m—R80;
or R1 and R2, or R3 and R4, or both, taken together represent a ring having 5-7 atoms in the backbone of said ring;
said ring having zero, one or two heteroatoms in its backbone;
and said ring is substituted or unsubstituted;
R5 and R6, for each occurrence, independently represent halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or —(CH2)m—R80;
the B and B′ rings of the binaphthyl core independently are unsubstituted or substituted with R5 and R6 respectively, any number of times up to the limitations imposed by stability and the rules of valence;
R80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl;
m is independently for each occurrence an integer in the range 0 to 8 inclusive;
and
the ligand, when chiral, is mixture of enantiomers or a single enantiomer;
wherein
R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and —(CH2)m—R80;
the A and A′ rings of the biphenyl core independently are unsubstituted or substituted with R1 and R2, respectively, any number of times up to the limitations imposed by stability and the rules of valence;
R1 and R2 are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, —SiR3, and —(CH2)m—R80;
R80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl;
m is independently for each occurrence an integer in the range 0 to 8 inclusive;
and
the ligand, when chiral, is mixture of enantiomers or a single enantiomer;
wherein
R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and —(CH2)m—R80;
the A, B, A′, and B′ rings of the binaphthyl core independently are unsubstituted or substituted with R1, R2, R3, and R4, respectively, any number of times up to the limitations imposed by stability and the rules of valence;
R1, R2, R3, and R4, are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, —SiR3, and —(CH2)m—R80;
R80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl;
m is independently for each occurrence an integer in the range 0 to 8 inclusive;
and
the ligand, when chiral, is mixture of enantiomers or a single enantiomer;
wherein
R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and —(CH2)m—R80;
the A and A′ rings of the biphenyl core independently are unsubstituted or substituted with R1 and R2, respectively, any number of times up to the limitations imposed by stability and the rules of valence;
R1 and R2 are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, —SiR3, and —(CH2)m—R80;
R80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl;
m is independently for each occurrence an integer in the range 0 to 8 inclusive;
and
the ligand, when chiral, is mixture of enantiomers or a single enantiomer;
wherein
R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and —(CH2)m—R80;
the A, B, A′, and B′ rings of the binaphthyl core independently are unsubstituted or substituted with R1, R2, R3, and R4, respectively, any number of times up to the limitations imposed by stability and the rules of valence;
R1, R2, R3, and R4, are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, —SiR3, and —(CH2)m—R80;
R80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl;
m is independently for each occurrence an integer in the range 0 to 8 inclusive;
and
the ligand, when chiral, is mixture of enantiomers or a single enantiomer;
and
the base is selected from the set consisting of carbonates, phosphates, fluorides, and alkoxides.

77 more elements

A method, comprising the step of:

combining a compound represented by ArX, a compound represented by RC(O)CH(R′)(R″), a transition metal, a ligand, and a base, thereby forming a compound represented by RC(O)CAr(R′)(R″):
wherein
Ar is selected from the set consisting of optionally substituted monocyclic and polycyclic aromatic and heteroaromatic moieties;
R, R′, and R″ are selected, independently for each occurrence, from the set consisting of H, alkyl, heteroalkyl, aralkyl, aryl, heteroaryl;
X is selected from the set consisting of Cl, and Br;
Ar and one of R, R′, and R″ may be covalently linked such that the reaction is intramolecular;
the transition metal is palladium;
the ligand of the present invention is selected from the group consisting of structures 1-7 inclusive:
wherein
A and B independently represent fused rings selected from the group consisting of monocyclic or polycyclic cycloalkyls, cycloalkenyls, aryls, and heterocyclic rings, said rings having 4 to 8 backbone atoms;
X and Y represent, independently for each occurrence, N, P, As, OR, or SR;
R, R1, R2, R3, and R4, for each occurrence, independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or —(CH2)m—R80;
R5 and R6, for each occurrence, independently represent halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or —(CH2)m—R80;
A and B independently are unsubstituted or substituted with R5 and R6, respectively, any number of times up to the limitations imposed by stability and the rules of valence;
R1 and R2, or R3 and R4, or both, taken together optionally represent a ring having 5-7 atoms in the backbone of said ring;
said ring having zero, one or two heteroatoms in its backbone;
and said ring is substituted or unsubstituted;
R80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl;
m is independently for each occurrence an integer in the range 0 to 8 inclusive;
and
the ligand, when chiral, is mixture of enantiomers or a single enantiomer;
wherein
X and Y represent, independently for each occurrence, N, P, As, OR, or SR;
R, R1, R2, R3, R4, R5, R6, R7, and R8, for each occurrence, independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or —(CH2)m—R80;
or two substituents, with an ortho-relationship therebetween, selected from the group consisting of R1, R2, R3, R4, R5, R6, R7, and R8, taken together, represent a ring having 5-7 atoms in the backbone of said ring;
said ring having zero, one or two heteroatoms in its backbone;
and said ring is substituted or unsubstituted;
R80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl;
m is independently for each occurrence an integer in the range 0 to 8 inclusive;
and
the ligand, when chiral, is mixture of enantiomers or a single enantiomer;
wherein
X and Y represent, independently for each occurrence, N, P, As, OR, or SR;
R, R1, R2, R3, and R4, for each occurrence, independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or —(CH2)m—R80;
or R1 and R2, or R3 and R4, or both, taken together represent a ring having 5-7 atoms in the backbone of said ring;
said ring having zero, one or two heteroatoms in its backbone;
and said ring is substituted or unsubstituted;
R5 and R6, for each occurrence, independently represent halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or —(CH2)m—R80;
the B and B′ rings of the binaphthyl core independently are unsubstituted or substituted with R5 and R6, respectively, any number of times up to the limitations imposed by stability and the rules of valence;
R80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl;
m is independently for each occurrence an integer in the range 0 to 8 inclusive;
and
the ligand, when chiral, is mixture of enantiomers or a single enantiomer;
wherein
R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and —(CH2)m—R80;
the A and A′ rings of the biphenyl core independently are unsubstituted or substituted with R1 and R2, respectively, any number of times up to the limitations imposed by stability and the rules of valence;
R1 and R2 are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, —SiR3, and —(CH2)m—R80;
R80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl;
m is independently for each occurrence an integer in the range 0 to 8 inclusive;
and
the ligand, when chiral, is mixture of enantiomers or a single enantiomer;
wherein
R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and —(CH2)m—R80;
the A, B, A′, and B′ rings of the binaphthyl core independently are unsubstituted or substituted with R1, R2, R3, and R4, respectively, any number of times up to the limitations imposed by stability and the rules of valence;
R1, R2, R3, and R4, are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, —SiR3, and —(CH2)m—R80;
R80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl;
m is independently for each occurrence an integer in the range 0 to 8 inclusive;
and
the ligand, when chiral, is mixture of enantiomers or a single enantiomer;
wherein
R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and —(CH2)m—R80;
the A and A′ rings of the biphenyl core independently are unsubstituted or substituted with R1 and R2, respectively, any number of times up to the limitations imposed by stability and the rules of valence;
R1 and R2 are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, —SiR3, and —(CH2)m—R80;
R80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl;
m is independently for each occurrence an integer in the range 0 to 8 inclusive;
and
the ligand, when chiral, is mixture of enantiomers or a single enantiomer;
wherein
R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and —(CH2)m—R80;
the A, B, A′, and B′ rings of the binaphthyl core independently are unsubstituted or substituted with R1, R2, R3, and R4, respectively, any number of times up to the limitations imposed by stability and the rules of valence;
R1, R2, R3, and R4, are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, —SiR3, and —(CH2)m—R80;
R80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl;
m is independently for each occurrence an integer in the range 0 to 8 inclusive;
and
the ligand, when chiral, is mixture of enantiomers or a single enantiomer;
and
the base is selected from the set consisting of carbonates, phosphates, fluorides, and alkoxides.

74 more elements

Dependencies are inferred from the claim text.

Facts

Application: 11/229,043Filed 16 Sep 2005 · continuation
Priority: 10 Jul 1998
Published: US 2006/0069257 A130 Mar 2006
Granted: 24 Jul 2007
Term ends: Not estimatedThe source records don’t support an estimate.

Classification65 codes

C07C 1/26
Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon: starting from organic compounds containing only halogen…
C07C 1/321
Starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen: the hetero-atom being a non-metal atom
C07C 17/16
By replacement by halogens: of hydroxyl groups
C07C 17/263
By reactions involving an increase in the number of carbon atoms in the skeleton: by condensation reactions

Family

Application09/113,478Parent of this continuation-in-part · filed 10 Jul 1998
Application09/231,315Parent of this continuation · filed 13 Jan 1999
Application10/004,101Parent of this division · filed 23 Oct 2001
Application10/420,950Parent of this continuation · filed 22 Apr 2003
US 2006/0069257 A1Pre-grant publication · published 30 Mar 2006
US 6,946,560 B2Parent of this continuation
Application10/420,950Parent of this division
US 6,307,087 B1Parent of this continuation
Application10/004,101Parent of this continuation
US 6,395,916 B1Parent of this continuation-in-part
Application09/231,315Parent of this continuation-in-part
US 2002/0156295 A1Published application
US 2004/0010149 A1Published application
US 7,026,498 B2Related patent
US 7,247,731 B2This patent

From the US filing history. Foreign family members aren’t listed.

Timeline

Citations

Open elsewhere

patentgrep

Loading patent…

Abstract

A method, comprising the step of:

combining a compound represented by ArX, a compound represented by HN(R′)R″, a transition metal, a ligand, and a base, thereby forming a compound represented by ArN(R′)R″:
wherein
Ar is selected from the set consisting of optionally substituted monocyclic and polycyclic aromatic and heteroaromatic moieties;
X is selected from the set consisting of Cl, and Br;
R′ and R″ are selected, independently for each occurrence, from the set consisting of H, alkyl, heteroalkyl, aryl, heteroaryl, aralkyl, alkoxyl, amino, trialkylsilyl, and triarylsilyl;
R′ and R″, taken together, may form an optionally substituted ring consisting of 3-10 backbone atoms inclusive;
said ring optionally comprising one or more heteroatoms beyond the nitrogen to which R′ and R″ are bonded;
R′ and/or R″ may be covalently linked to Ar such that the amination reaction is intramolecular;
the transition metal is palladium;
the ligand of the present invention is selected from the group consisting of structures 1-7 inclusive:
wherein
A and B independently represent fused rings selected from the group consisting of monocyclic or polycyclic cycloalkyls, cycloalkenyls, aryls, and heterocyclic rings, said rings having 4 to 8 backbone atoms;
X and Y represent, independently for each occurrence, N, P, As, OR, or SR;
R, R1, R2, R3, and R4, for each occurrence, independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or —(CH2)m—R80;
R5 and R6, for each occurrence, independently represent halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or —(CH2)m—R80;
A and B independently are unsubstituted or substituted with R5 and R6, respectively, any number of times up to the limitations imposed by stability and the rules of valence;
R1 and R2, or R3 and R4, or both, taken together optionally represent a ring having 5-7 atoms in the backbone of said ring;
said ring having zero, one or two heteroatoms in its backbone;
and said ring is substituted or unsubstituted;
R80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl;
m is independently for each occurrence an integer in the range 0 to 8 inclusive;
and
the ligand, when chiral, is mixture of enantiomers or a single enantiomer;
wherein
X and Y represent, independently for each occurrence, N, P, As, OR, or SR;
R, R1, R2, R3, R4, R5, R6, R7, and R8, for each occurrence, independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or —(CH2)m—R80;
or two substituents, with an ortho-relationship therebetween, selected from the group consisting of R1, R2, R3, R4, R5, R6, R7, and R8, taken together, represent a ring having 5-7 atoms in the backbone of said ring;
said ring having zero, one or two heteroatoms in its backbone;
and said ring is substituted or unsubstituted;
R80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl;
m is independently for each occurrence an integer in the range 0 to 8 inclusive;
and
the ligand, when chiral, is mixture of enantiomers or a single enantiomer;
wherein
X and Y represent, independently for each occurrence, N, P, As, OR, or SR;
R, R1, R2, R3, and R4, for each occurrence, independently represent hydrogen, halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or —(CH2)m—R80;
or R1 and R2, or R3 and R4, or both, taken together represent a ring having 5-7 atoms in the backbone of said ring;
said ring having zero, one or two heteroatoms in its backbone;
and said ring is substituted or unsubstituted;
R5 and R6, for each occurrence, independently represent halogen, alkyl, alkenyl, alkynyl, hydroxyl, alkoxyl, silyloxy, amino, nitro, sulfhydryl, alkylthio, imine, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, carboxamide, anhydride, silyl, thioalkyl, alkylsulfonyl, arylsulfonyl, selenoalkyl, ketone, aldehyde, guanidine, amidine, acetal, ketal, amine oxide, aryl, azide, carbamate, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or —(CH2)m—R80;
the B and B′ rings of the binaphthyl core independently are unsubstituted or substituted with R5 and R6, respectively, any number of times up to the limitations imposed by stability and the rules of valence;
R80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl;
m is independently for each occurrence an integer in the range 0 to 8 inclusive;
and
the ligand, when chiral, is mixture of enantiomers or a single enantiomer;
wherein
R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and —(CH2)m—R80;
the A and A′ rings of the biphenyl core independently are unsubstituted or substituted with R1 and R2, respectively, any number of times up to the limitations imposed by stability and the rules of valence;
R1 and R2 are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, —SiR3, and —(CH2)m—R80;
R80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl;
m is independently for each occurrence an integer in the range 0 to 8 inclusive;
and
the ligand, when chiral, is mixture of enantiomers or a single enantiomer;
wherein
R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and —(CH2)m—R80;
the A, B, A′, and B′ rings of the binaphthyl core independently are unsubstituted or substituted with R1, R2, R3, and R4, respectively, any number of times up to the limitations imposed by stability and the rules of valence;
R1, R2, R3, and R4, are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, —SiR3, and —(CH2)m—R80;
R80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl;
m is independently for each occurrence an integer in the range 0 to 8 inclusive;
and
the ligand, when chiral, is mixture of enantiomers or a single enantiomer;
wherein
R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and —(CH2)m—R80;
the A and A′ rings of the biphenyl core independently are unsubstituted or substituted with R1 and R2, respectively, any number of times up to the limitations imposed by stability and the rules of valence;
R1 and R2 are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, —SiR3, and —(CH2)m—R80;
R80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl;
m is independently for each occurrence an integer in the range 0 to 8 inclusive;
and
the ligand, when chiral, is mixture of enantiomers or a single enantiomer;
wherein
R is selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, and —(CH2)m—R80;
the A, B, A′, and B′ rings of the binaphthyl core independently are unsubstituted or substituted with R1, R2, R3, and R4, respectively, any number of times up to the limitations imposed by stability and the rules of valence;
R1, R2, R3, and R4, are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, —SiR3, and —(CH2)m—R80;
R80 represents independently for each occurrence unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, or polycyclyl;
m is independently for each occurrence an integer in the range 0 to 8 inclusive;
and
the ligand, when chiral, is mixture of enantiomers or a single enantiomer;
and
the base is selected from the set consisting of carbonates, phosphates, fluorides, and alkoxides.

76 more elements

Facts

Application

11/229,043Filed 16 Sep 2005 · continuation

Priority

10 Jul 1998

Published

US 2006/0069257 A130 Mar 2006

Granted

24 Jul 2007

Term ends

Not estimatedThe source records don’t support an estimate.

Classification65 codes

C07C 1/26
Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon: starting from organic compounds containing only halogen…
C07C 1/321
Starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen: the hetero-atom being a non-metal atom
C07C 17/16
By replacement by halogens: of hydroxyl groups
C07C 17/263
By reactions involving an increase in the number of carbon atoms in the skeleton: by condensation reactions

Family

Application09/113,478Parent of this continuation-in-part · filed 10 Jul 1998

Application09/231,315Parent of this continuation · filed 13 Jan 1999

Application10/004,101Parent of this division · filed 23 Oct 2001

Application10/420,950Parent of this continuation · filed 22 Apr 2003

US 2006/0069257 A1Pre-grant publication · published 30 Mar 2006

US 6,946,560 B2Parent of this continuation

Application10/420,950Parent of this division

US 6,307,087 B1Parent of this continuation

Application10/004,101Parent of this continuation

US 6,395,916 B1Parent of this continuation-in-part

Application09/231,315Parent of this continuation-in-part

US 2002/0156295 A1Published application

US 2004/0010149 A1Published application

US 7,026,498 B2Related patent

US 7,247,731 B2This patent

From the US filing history. Foreign family members aren’t listed.