IP Library › Granted Patent US 7,247,731

Granted Patent B2

US 7,247,731 · App. 11/229,043 · Granted Jul 24, 2007

Ligands for metals and improved metal-catalyzed processes based thereon

Assignee: Massachusetts Institute of Technology

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Patent No.: US 7,247,731
App. No.: 11/229,043
Granted: Jul 24, 2007
Kind: B2

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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.

Claims (265)

1. 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 5 and R 6 , 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 —(CH 2 ) m —R 80 ;

A and B independently are unsubstituted or substituted with R 5 and R 6 , respectively, any number of times up to the limitations imposed by stability and the rules of valence;

R 1 and R 2 , or R 3 and R 4 , 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;

R 80 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, R 1 , R 2 , R 3, R 4 , R 5 , R 6 , R 7 , and R 8 , 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 —(CH 2 ) m —R 80 ; or two substituents, with an ortho-relationship therebetween, selected from the group consisting of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 , 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;

R 80 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;

the B and B′ rings of the binaphthyl core independently are unsubstituted or substituted with R 5 and R 6 , respectively, any number of times up to the limitations imposed by stability and the rules of valence;

R 80 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 —(CH 2 ) m —R 80 ;

the A and A′ rings of the biphenyl core independently are unsubstituted or substituted with R 1 and R 2 , respectively, any number of times up to the limitations imposed by stability and the rules of valence;

R 1 and R 2 are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, —SiR 3 , and —(CH 2 ) m —R 80 ;

R 80 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 —(CH 2 ) m —R 80 ;

the A, B, A′, and B′ rings of the binaphthyl core independently are unsubstituted or substituted with R 1 , R 2 , R 3 , and R 4 , respectively, any number of times up to the limitations imposed by stability and the rules of valence;

R 1 , R 2 , R 3 , and R 4 , are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, —SiR 3 , and —(CH 2 ) m —R 80 ;

R 80 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 —(CH 2 ) m —R 80 ;

R 1 and R 2 are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, —SiR 3 , and —(CH 2 ) m —R 80 ;

R 80 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 —(CH 2 ) m —R 80 ;

R 1 , R 2 , R 3 , and R 4 , are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, —SiR 3 , and —(CH 2 ) m —R 80 ;

R 80 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.

2. 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

X and Y represent, independently for each occurrence, N, P, As, OR, or SR;

R 5 and R 6 , 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 —(CH 2 ) m —R 80 ;

A and B independently are unsubstituted or substituted with R 5 and R 6 , respectively, any number of times up to the limitations imposed by stability and the rules of valence;

R 80 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, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 , 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 —(CH 2 ) m —R 80 ; or two substituents, with an ortho-relationship therebetween, selected from the group consisting of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 , 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;

R 80 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 80 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 —(CH 2 ) m —R 80 ;

R 1 and R 2 are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, —SiR 3 , and —(CH 2 ) m —R 80 ;

R 80 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 —(CH 2 ) m —R 80 ;

R 1 , R 2 , R 3 , and R 4 , are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, —SiR 3 , and —(CH 2 ) m —R 80 ;

R 80 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 —(CH 2 ) m —R 80 ;

R 1 and R 2 are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, —SiR 3 , and —(CH 2 ) m —R 80 ;

R 80 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 —(CH 2 ) m —R 80 ;

R 1 , R 2 , R 3 , and R 4 , are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, —SiR 3 , and —(CH 2 ) m —R 80 ;

R 80 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.

3. 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

X and Y represent, independently for each occurrence, N, P, As, OR, or SR;

A and B independently are unsubstituted or substituted with R 5 and R 6 , respectively, any number of timesup to the limitations imposed by stability and the rules of valence;

R 80 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, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 , 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 —(CH 2 ) m —R 80 ; or two substituents, with an ortho-relationship therebetween, selected from the group consisting of R 1 , R 2 , R 3 R 4 , R 5 , R 6 , R 7 , and R 8 , 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;

R 80 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, R 1 , R 2 , R 3 , and R 4 , 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 —(CH 2 ) m —R 80 ; or R 1 and R 2 , or R 3 and R 4 , 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; R 5 and R 6 , 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 —(CH 2 ) m —R 80 ;

the B and B′ rings of the binaphthyl core independently are unsubstituted or substituted with R 5 and R 6 respectively, any number of times up to the limitations imposed by stability and the rules of valence;

R 80 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 —(CH 2 ) m —R 80 ;

R 1 and R 2 are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, —SiR 3 , and —(CH 2 ) m —R 80 ;

R 80 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 —(CH 2 ) m —R 80 ;

R 1 , R 2 , R 3 , and R 4 , are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, —SiR 3 , and —(CH 2 ) m —R 80 ;

R 80 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 —(CH 2 ) m —R 80 ;

R 1 and R 2 are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, —SiR 3 , and —(CH 2 ) m —R 80 ;

R 80 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 —(CH 2 ) m —R 80 ;

R 1 , R 2 , R 3 , and R 4 , are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, —SiR 3 , and —(CH 2 ) m —R 80 ;

R 80 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.

4. 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

X and Y represent, independently for each occurrence, N, P, As, OR, or SR;

A and B independently are unsubstituted or substituted with R 5 and R 6 , respectively, any number of times up to the limitations imposed by stability and the rules of valence;

R 80 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, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 , 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 —(CH 2 ) m —R 80 ; or two substituents, with an ortho-relationship therebetween, selected from the group consisting of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 , 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;

R 80 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 80 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 —(CH 2 ) m —R 80 ;

R 1 and R 2 are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, —SiR 3 , and —(CH 2 ) m —R 80 ;

R 80 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 —(CH 2 ) m —R 80 ;

R 1 , R 2 , R 3 , and R 4 , are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, —SiR 3 , and —(CH 2 ) m —R 80 ;

R 80 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 —(CH 2 ) m —R 80 ;

R 1 and R 2 are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, —SiR 3 , and —(CH 2 ) m —R 80 ;

R 80 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 —(CH 2 ) m —R 80 ;

R 1 , R 2 , R 3 , and R 4 , are selected, independently for each occurrence, from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, halogen, —SiR 3 , and —(CH 2 ) m —R 80 ;

R 80 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.

5. The method of claim 1 , wherein X is Cl.

6. The method of claim 1 , wherein the base is sodium carbonate, cesium carbonate, potassium phosphate, potassium fluoride, cesium fluoride, or sodium tert-butoxide.

7. The method of claim 1 , wherein the ligand is 2-dicyclohexylphosphino-2′-dimethylamino-biphenyl.

8. The method of claim 1 , wherein X is Cl; and the base is sodium carbonate, cesium carbonate, potassium phosphate, potassium fluoride, cesium fluoride, or sodium tert-butoxide.

9. The method of claim 1 , wherein X is Cl; the base is sodium carbonate, cesium carbonate, potassium phosphate, potassium fluoride, cesium fluoride, or sodium tert-butoxide; and the ligand is 2-dicyclohexylphosphino-2′-dimethylamino-biphenyl.

10. The method of claim 2 , wherein X is Cl.

11. The method of claim 2 , wherein the base is sodium carbonate, cesium carbonate, potassium phosphate, potassium fluoride, cesium fluoride, or sodium tert-butoxide.

12. The method of claim 2 , wherein the ligand is 2-dicyclohexylphosphino-2′-dimethylamino-biphenyl.

13. The method of claim 2 , wherein X is Cl; and the base is sodium carbonate, cesium carbonate, potassium phosphate, potassium fluoride, cesium fluoride, or sodium tert-butoxide.

14. The method of claim 2 , wherein X is Cl; the base is sodium carbonate, cesium carbonate, potassium phosphate, potassium fluoride, cesium fluoride, or sodium tert-butoxide; and the ligand is 2-dicyclohexylphosphino-2′-dimethylamino-biphenyl.

15. The method of claim 3 , wherein X is Cl.

16. The method of claim 3 , wherein the base is sodium carbonate, cesium carbonate, potassium phosphate, potassium fluoride, cesium fluoride, or sodium tert-butoxide.

17. The method of claim 3 , wherein the ligand is 2-dicyclohexylphosphino-2′-dimethylamino-biphenyl.

18. The method of claim 3 , wherein X is Cl; and the base is sodium carbonate, cesium carbonate, potassium phosphate, potassium fluoride, cesium fluoride, or sodium tert-butoxide.

19. The method of claim 3 , wherein X is Cl; the base is sodium carbonate, cesium carbonate, potassium phosphate, potassium fluoride, cesium fluoride, or sodium tert-butoxide; and the ligand is 2-dicyclohexylphosphino-2′-dimethylamino-biphenyl.

20. The method of claim 4 , wherein X is Cl.

21. The method of claim 4 , wherein the base is sodium carbonate, cesium carbonate, potassium phosphate, potassium fluoride, cesium fluoride, or sodium tert-butoxide.

22. The method of claim 4 , wherein the ligand is 2-dicyclohexylphosphino-2′-dimethylamino-biphenyl.

23. The method of claim 4 , wherein X is Cl; and the base is sodium carbonate, cesium carbonate, potassium phosphate, potassium fluoride, cesium fluoride, or sodium tert-butoxide.

24. The method of claim 4 , wherein X is Cl; the base is sodium carbonate, cesium carbonate, potassium phosphate, potassium fluoride, cesium fluoride, or sodium tert-butoxide; and the ligand is 2-dicyclohexylphosphino-2′-dimethylamino-biphenyl.

Assignments (1)

CONFIRMATORY LICENSE Recorded May 25, 2011

From: MASSACHUSETTS INSTITUTE OF TECHNOLOGY

To: NATIONAL SCIENCE FOUNDATION

Reel/Frame 026332/0611 →

Continuity (5)

Continuation 1042095000 · Apr 22, 2003

Division 1000410100 · Oct 23, 2001

Continuation 0923131500 · Jan 13, 1999

Continuation In Part 0911347800 · Jul 10, 1998

Related Publication 20060069257A1 · Mar 30, 2006