Ligands for metals and improved metal-catalyzed processes based thereon

The ligand represented by structure 2:

• wherein
• X represents PR2;
• Y represents H, NR2, OR, or SR;
• R represents, independently for each occurrence, alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl, heteroaralkyl, or —(CH2)m—R80;
• 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, ester, heteroalkyl, nitrile, guanidine, amidine, acetal, ketal, amine oxide, aryl, heteroaryl, azide, aziridine, carbamate, epoxide, hydroxamic acid, imide, oxime, sulfonamide, thioamide, thiocarbamate, urea, thiourea, or —(CH2)m—R80;
• one or more pairs of substituent, with an ortho-relationship therebetween, selected from the group consisting of R1, R2, R3, R4, R5, R6, R7, and R8, taken together optionally represent a ring having a total of 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 an unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, heterocycle, or polycycle;
• m is an integer in the range 0 to 8 inclusive;
• and
• the ligand, when chiral, is a mixture of enantiomers or a single enantiomer.

The ligand represented by structure 3:

• wherein
• X represents NR2, P(alkyl)2, P(cycloalkyl)2, AsR2, or OR;
• Y represents H, alkyl, NR2, AsR2, or OR;
• X and Y are not identical;
• 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, ester, heteroalkyl, nitrile, guanidine, amidine, acetal, ketal, amine oxide, aryl, heteroaryl, azide, aziridine, carbamate, epoxide, 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, ester, heteroalkyl, nitrile, guanidine, amidine, acetal, ketal, amine oxide, aryl, heteroaryl, azide, aziridine, carbamate, epoxide, 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;
• R1 and R2, or R3 and R4, or both, taken together optionally represent a ring consisting of a total of 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 an unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, heterocycle, or polycycle;
• m is an integer in the range 0 to 8 inclusive;
• and
• the ligand, when chiral, is a mixture of enantiomers or a single enantiomer.

The ligand represented by structure 4:

• wherein
• R is selected, independently for each occurrence, from the group consisting of alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl, heteroaralkyl, 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, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl, heteroaralkyl, halogen, —SiR3, and —(CH2)m—R80;
• R80 represents an unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, heterocycle, or polycycle;
• m is an integer in the range 0 to 8 inclusive;
• and
• the ligand, when chiral, is a mixture of enantiomers or a single enantiomer.

The ligand represented by structure 5:

• wherein
• R is selected, independently for each occurrence, from the group consisting of alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl, heteroaralkyl, 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, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl, heteroaralkyl, halogen, —SiR3, and —(CH2)m—R80;
• R80 represents an unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, heterocycle, or polycycle;
• m is an integer in the range 0 to 8 inclusive;
• and
• the ligand, when chiral, is a mixture of enantiomers or a single enantiomer;
• provided that when R is cycloalkyl or aryl, there is at least one instance of R1, R2, R3, or R4.

The ligand represented by structure 7:

• wherein
• R is selected, independently for each occurrence, from the group consisting of alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl, heteroaralkyl, and —(CH2)m—R80;
• P(R)2 represents P(alkyl)2, or P(cycloalkyl)2;
• 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, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl, heteroaralkyl, halogen, —SiR3, and —(CH2)m—R80;
• R80 represents an unsubstituted or substituted aryl, cycloalkyl, cycloalkenyl, heterocycle, or polycycle;
• m is an integer in the range 0 to 8 inclusive;
• and
• the ligand, when chiral, is a mixture of enantiomers or a single enantiomer.

The method depicted in Scheme 1:

• 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, Br, I, —OS(O)2alkyl, and —OS(O)2aryl;
• 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 selected from the set consisting of the Group VIIIA metals;
• the ligand is selected from the set consisting of 1-7 inclusive;
• and
• the base is selected from the set consisting of hydrides carbonates, phosphates, alkoxides, amides, carbanions, and silyl anions.

The method depicted in Scheme 2:

• 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, Br, I, —OS(O)2alkyl, and —OS(O)2aryl;
• Ar and Ar′ may be covalently linked such that the reaction is intramolecular;
• the transition metal is selected from the set consisting of the Group VIIIA metals;
• the ligand is selected from the set consisting of 1-7 inclusive;
• and
• the base is selected from the set consisting of carbonates, phosphates, fluorides, alkoxides, amides, carbanions, and silyl anions.

The method depicted in Scheme 3:

• 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, Br, I, —OS(O)2alkyl, and —OS(O)2aryl;
• Ar and R may be covalently linked such that the reaction is intramolecular;
• the transition metal is selected from the set consisting of the Group VIIIA metals;
• the ligand is selected from the set consisting of 1-7 inclusive;
• and
• the base is selected from the set consisting of carbonates, phosphates, fluorides, alkoxides, amides, carbanions, and silyl anions.

The method depicted in Scheme 4:

• 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, Br, I, —OS(O)2alkyl, and —OS(O)2aryl;
• Ar and one of R, R′, and R″ may be covalently linked such that the reaction is intramolecular;
• the transition metal is selected from the set consisting of the Group VIIIA metals;
• the ligand is selected from the set consisting of 1-7 inclusive;
• and
• the base is selected from the set consisting of carbonates, phosphates, fluorides, alkoxides, amides, carbanions, and silyl anions.