Kinetic Resolution of Racemic Aldehydes through Asymmetric Allenoate γ-Addition: Synthesis of (+)-Xylogiblactone A.

Abstract

A synthesis of (+)-xylogiblactone A has been achieved from t-butyl 2-methylbuta-2,3-dienoate in a linear three-step sequence. The key elements of the synthesis include a kinetic resolution of racemic 2-silyoxyaldehyde through the allenoate γ-addition to yield the γ-adduct as a single isomer and the subsequent gold catalysis to form the butenolide core. For a general method, the kinetic resolution of several racemic 2-silyloxyaldehydes is also performed to provide products in high levels of stereoselectivity with unusual anti-Felkin-Anh addition fashion.