Enantiomer differentiation in intramolecular carbon-hydrogen insertion reactions of racemic secondary alkyl diazoacetates catalyzed by chiral dirhodium(II) carboxamidates

Highly efficient kinetic resolution of racemic secondary alkyl diazoacetates in intramolecular carbon-hydrogen insertion reactions has been achieved using chiral dirhodium(II) carboxamidates. Products formed from catalytic diazo decomposition of racemic 2-octyl diazoacetate and, separately, its (2R)- and (2S)-enantiomeric forms, as well as both cis- and trans-2-methylcyclohexyl diazoacetates, have been systematically evaluated. Enantioselectivities up to 99 % ee have been obtained for gamma-lactone formation. beta-lactone production has been observed and, although minor with cyclohexyl diazoacetates, is the major insertion pathway for diazo decomposition of 2-octyl diazoacetate.