Synthesis of alpha-Nitro-alpha-diazocarbonyl Derivatives and Their Applications in the Cyclopropanation of Alkenes and in O-H Insertion Reactions

摘要

A facile and highly efficient method for the preparation of alpha-nitro-alpha-diazocarbonyl derivatives by a diazo-transfer reaction involving (trifluromethyl)sulfonyl azide has been developed. These substrates undergo a rhodium-catalyzed cyclopropanation reaction with a variety of alkenes. A systematic study of the reaction indicated that the diastereoselectivity of the cyclopanation could be effectively controlled through the modification of the steric bulk of the diazo reagent. A novel O-H insertion reaction of the metal-carbene complex derived from the alpha-nitro-alpha-diazocarbonyl reagent afforded the corresponding novel alpha-nitro-alpha-alkoxy carbonyl derivatives.