Ring expansion of 5- to 6-member zirconacycles by carbenoid insertion

Abstract

A wide range of carbenoids (1-lithio-1-halo species), including those with α-SiR 3, OEt, SPh, SO 2Ph, P(O)(OEt) 2, and CN substituents, insert into 5-member zirconacycles (saturated and unsaturated, mono- and bi-cyclic) to afford functionalized 6-member zirconacycles. 1-Lithio-1-haloalkenes insert to afford 6-member zirconacycles with an alkylidene substituent next to the metal. Unexpected double insertion of some carbenoids, and evidence for endocylic β-hydride transfer processes provide additional mechanistic interest.