Copper-catalyzed formation of carbon-heteroatom and carbon-carbon bonds

A method represented by Scheme 2:

• wherein
• X represents I, Br, Cl, alkylsulfonate, or arylsulfonate;
• Z represents optionally substituted aryl, heteroaryl or alkenyl;
• catalyst consists essentially of a copper atom or ion, and at least one ligand, wherein said at least one ligand is 1,10-phenanthroline;
• base represents a Bronsted base;
• R represents alkyl, cycloalkyl, aralkyl, heteroaryl, formyl, acyl, alkylO2C—, arylO2C—, heteroarylO2C—, aralkylO2C—, heteroaralkylO2C—, acyl(R′)N—, alkylOC(O)N(R′)—, arylOC(O)N(R′)—, aralkylOC(O)N(R′)—, heteroaralkylOC(O)N(R′)—, —N═C(alkyl)2, or —N═C(aryl)2;
• R′ represents H, alkyl, cycloalkyl, aralkyl, heteroaralkyl, aryl, heteroaryl, formyl, acyl, amino, or —C(NR″)N(R″)2;
• R″ represents independently for each occurrence H, alkyl, cycloalkyl, aryl, heteroaryl, aralkyl or heteroaralkyl;
• R and R′ taken together may represent ═C(alkyl)2, or ═C(aryl)2;
• and
• R and R′ are optionally connected by a covalent bond;
• provided that R and R′ are not connected by a covalent bond when R and R′ are both either aryl or heteroaryl;
• provided that when R is aryl or heteroaryl, R′ is not formyl or acyl;
• further provided that when R is formyl or acyl, R′ is not aryl or heteroaryl.

A method represented by Scheme 3:

• wherein
• X represents I, Br, Cl, alkylsulfonate, or arylsulfonate;
• Z represents optionally substituted aryl, heteroaryl or alkenyl;
• catalyst consists essentially of a copper atom or ion, and at least one ligand selected from the group consisting of optionally substituted alkyl amine;
• base is a carbonate, phosphate, oxide, hydroxide, alkoxide, aryloxide, metal amide, fluoride, or guanidine;
• R represents alkyl, cycloalkyl, aralkyl, aryl, heteroaryl, formyl, acyl, alkylO2C—, arylO2C—, heteroarylO2C—, aralkylO2C—, heteroaralkylO2C—, acyl(R′)N—, alkylOC(O)N(R′)—, arylOC(O)N(R′)—, aralkylOC(O)N(R′)—, heteroaralkylOC(O)N(R′)—, —N═C(alkyl)2, or —N═C(aryl)2;
• R′ represents H, alkyl, cycloalkyl, aralkyl, heteroaralkyl, aryl, heteroaryl, formyl, acyl, amino, or —C(NR″)N(R″)2;
• R″ represents independently for each occurrence H, alkyl, cycloalkyl, aryl, heteroaryl, aralkyl or heteroaralkyl;
• R and R′ taken together may represent ═C(alkyl)2, or ═C(aryl)2;
• and
• R and R′ are optionally connected by a covalent bond;
• provided that R and R′ are not connected by a covalent bond when R and R′ are both either aryl or heteroaryl;
• provided that when R is aryl or heteroaryl, R′ is not formyl or acyl;
• further provided that when R is formyl or acyl, R′ is not aryl or heteroaryl.