Silver-Catalyzed Regio- and Stereoselective Formal Carbene Insertion into Unstrained C−C σ-Bonds of 1,3-Dicarbonyls

Abstract

Summary: A regio- and stereoselective silver-catalyzed formal carbene insertion into 1,3-dicarbonyls has been developed, using N-nosylhydrazones as diazo surrogates. Two new C−C bonds are constructed at the carbenic carbon center through the selective cleavage of the C−C(=O) σ-bond of acyclic 1,3-dicarbonyls, enabling the preparation of various synthetically useful polysubstituted γ-diketones, γ-ketoesters, and γ-ketoamides in high yields. The in situ formation of a donor-acceptor cyclopropane, via reaction of the enolate of the 1,3-dicarbonyl with an electrophilic silver carbenoid, is proposed as a key process in the catalytic cycle. : Chemistry; Catalysis; Organic Synthesis Subject Areas: Chemistry, Catalysis, Organic Synthesis