Ligands for metals and improved metal-catalyzed processes based thereon

A method for forming a compound represented by ArN(R′)R″, 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;
• wherein
• Ar is selected from the group consisting of optionally substituted monocyclic and polycyclic aromatic and heteroaromatic moieties;
• X′ is selected from the group consisting of Cl, Br, I, —OS(O)2alkyl, and —OS(O)2aryl;
• R′ and R″ are selected, independently for each occurrence, from the group consisting of H, alkyl, heteroalkyl, aryl, heteroaryl, aralkyl, alkoxyl, amino, trialkylsilyl, and triarylsilyl;
• R′ and R″, taken together, optionally form an unsubstituted or substituted ring consisting of 3–10 backbone atoms inclusive;
• of which atoms zero, one or two atoms are heteroatoms beyond the nitrogen to which R′ and R″ are bonded;
• R′ and/or R″ may be covalently linked to Ar;
• the transition metal is selected from the group consisting of the Group VIIIA metals;
• the ligand is selected from the group consisting of a compound represented by 3:
• wherein
• X and Y represent, independently for each occurrence, N(R)2 or P(R)2;
• R, 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;
• R1, R2, R3, and R4, for each occurrence, independently represent hydrogen, halogen, alkyl, alkenyl, or aryl;
• R5 and R6, for each occurrence, independently represent halogen, alkyl, alkenyl, or aryl;
• the B and B′ rings of the binaphthyl core independently may be 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, and/or R3 and R4, taken together optionally represent a ring consisting of a total of 5–7 atoms in the backbone of said ring;
• of which atoms zero, one or two atoms are heteroatoms;
• and said ring is substituted or unsubstituted;
• R80 represents an unsubstituted or substituted aryl, a cycloalkyl, a cycloalkenyl, a heterocycle, or a polycycle;
• m is an integer in the range 0 to 8 inclusive;
• the ligand, when chiral, is a mixture of enantiomers or a single enantiomer;
• and
• the base is selected from the group consisting of hydrides, carbonates, phosphates, alkoxides, amides, carbanions, and silyl anions.

A method for forming a compound represented by Ar—Ar′, 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;
• wherein
• Ar and Ar′ are independently selected from the group consisting of optionally substituted monocyclic and polycyclic aromatic and heteroaromatic moieties;
• X′ is selected from the group consisting of Cl, Br, I, —OS(O)2alkyl, and —OS(O)2aryl;
• Ar and Ar′ may be covalently linked;
• the transition metal is selected from the group consisting of the Group VIIIA metals;
• the ligand is selected from the group consisting of a compound represented by 3:
• wherein
• X and Y represent, independently for each occurrence, N(R)2, or P(R)2;
• R, 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;
• R1, R2, R3, and R4, for each occurrence, independently represent hydrogen, halogen, alkyl, alkenyl, or aryl;
• R5 and R6, for each occurrence, independently represent halogen, alkyl, alkenyl, or aryl;
• the B and B′ rings of the binaphthyl core independently may be 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, and/or R3 and R4, taken together optionally represent a ring consisting of a total of 5–7 atoms in the backbone of said ring;
• of which atoms zero, one or two atoms are heteroatoms;
• and said ring is substituted or unsubstituted;
• R80 represents an unsubstituted or substituted aryl, a cycloalkyl, a cycloalkenyl, a heterocycle, or a polycycle;
• m is an integer in the range 0 to 8 inclusive;
• the ligand, when chiral, is a mixture of enantiomers or a single enantiomer;
• and
• the base is selected from the group consisting of carbonates, phosphates, fluorides, alkoxides, amides, carbanions, and silyl anions.

A method for forming a compound represented by Ar—R″, comprising the step of:

• combining a compound represented by ArX′, a compound represented by R″BR′2, a transition metal, a ligand and a base;
• wherein
• Ar is selected from the group consisting of optionally substituted monocyclic and polycyclic aromatic and heteroaromatic moieties;
• R″ is selected from the group consisting of optionally substituted alkyl, heteroalkyl, and aralkyl;
• R′ is selected, independently for each occurrence, from the group consisting of alkyl and heteroalkyl;
• the carbon-boron bond of said alkyl and heteroalkyl groups being inert under the reaction conditions;
• X′ is selected from the group consisting of Cl, Br, I, —OS(O)2alkyl, and —OS(O)2aryl;
• Ar and R″ may be covalently linked;
• the transition metal is selected from the group consisting of the Group VIIIA metals;
• the ligand is selected from the group consisting of a compound represented by 3:
• wherein
• X and Y represent, independently for each occurrence, N(R)2, or P(R)2;
• R, 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;
• R1, R2, R3, and R4, for each occurrence, independently represent hydrogen, halogen, alkyl, alkenyl, or aryl;
• R5 and R6, for each occurrence, independently represent halogen, alkyl, alkenyl, or aryl;
• the B and B′ rings of the binaphthyl core independently may be 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, and/or R3 and R4, taken together optionally represent a ring consisting of a total of 5–7 atoms in the backbone of said ring;
• of which atoms zero, one or two atoms are heteroatoms;
• and said ring is substituted or unsubstituted;
• R80 represents an unsubstituted or substituted aryl, a cycloalkyl, a cycloalkenyl, a heterocycle, or a polycycle;
• m is an integer in the range 0 to 8 inclusive
• the ligand, when chiral, is a mixture of enantiomers or a single enantiomer;
• and
• the base is selected from the set consisting of carbonates, phosphates, fluorides, alkoxides, amides, carbanions, and silyl anions.

A method for forming a compound represented by R′″C(O)C(R′)(R″)Ar, comprising the step of:

• combining a compound represented by ArX′, a compound represented by R′″C(O)CH(R′)R″, a transition metal, a ligand and a base;
• wherein
• Ar is selected from the group consisting of optionally substituted monocyclic and polycyclic aromatic and heteroaromatic moieties;
• R′, R″, and R′″ are selected, independently for each occurrence, from the group consisting of H, alkyl, heteroalkyl, aralkyl, aryl, and heteroaryl;
• X′ is selected from the group consisting of Cl, Br, I, —OS(O)2alkyl, and —OS(O)2aryl;
• Ar and one of R′, R″, and R′″ may be covalently linked;
• the transition metal is selected from the group consisting of the Group VIIIA metals;
• the ligand is selected from the group consisting of a compound represented by 3:
• wherein
• X and Y represent, independently for each occurrence, N(R)2, or P(R)2;
• R, 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;
• R1, R2, R3, and R4, for each occurrence, independently represent hydrogen, halogen, alkyl, alkenyl, or aryl;
• R5 and R6, for each occurrence, independently represent halogen, alkyl, alkenyl, or aryl;
• the B and B′ rings of the binaphthyl core independently maybe 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, and/or R3 and R4, taken together optionally represent a ring consisting of a total of 5–7 atoms in the backbone of said ring;
• of which atoms zero, one or two atoms are heteroatoms;
• and said ring is substituted or unsubstituted;
• R80 represents an unsubstituted or substituted aryl, a cycloalkyl, a cycloalkenyl, a heterocycle, or a polycycle;
• m is an integer in the range 0 to 8 inclusive;
• the ligand, when chiral, is a mixture of enantiomers or a single enantiomer;
• and
• the base is selected from the set consisting of carbonates, phosphates, fluorides, alkoxides, amides, carbanions, and silyl anions.