Marina N. Protopopova

Enantiocontrol and regiocontrol in lactam syntheses by intramolecular carbon-hydrogen insertion reactions of diazoacetamides catalyzed by chiral rhodium(II) carboxamides

Abstract Dirhodium(II) catalysts possessing chiral pyrrolidone or oxazolidinone ligands provide moderate enantiocontrol (up to 80% ee) in carbon-hydrogen insertion reactions of N -alkyl- N -( tert -butyl)diazoacetamides; substituents at the 2-position of the N -alkyl group control regioselectivity for β- and γ-lactam formation.

Enantioselective intramolecular cyclopropanation of N-allylic- and N-homoallylic diazoacetamides catalyzed by chiral dirhodium(II) catalysts

Abstract Diazodecomposition of N-(tert-butyl)-N-(3-buten-1-yl)diazoacetamides catalyzed by dirhodium(II) tetrakis[methyl 2-pyrrolidone-5(S)-carboxylate], Rh2(5S-MEPY)4, and tetrakis[methyl 2-oxazolidinone-4(S)-carboxylate], Rh2(4S-MEOX)4, forms products from intramolecular cyclopropanation in good yields with enantiomeric excesses ranging from 60–90%. Intramolecular cyclopropanation with N, N-diallyldiazoacetamide (72% ee) is competitive with intramolecular [3+2] dipolar cycloaddition.