Synthesis of chiral vinylic sulfoxides by Pd-catalyzed asymmetric sulfinylzincation

Abstract

Novel asymmetric sulfinylzincation of alkynoates has been accomplished via a Pd-catalyzed sulfinylzincation using 1-alkynyl sulfoxides bearing chiral auxiliaries as a sulfinylating reagent. The reaction proceeded in a highly syn-selective fashion, giving the ( E)-β-sulfinyl α,β-unsaturated ester exclusively. Among the chiral sulfinylating reagents tested, an isoborneol-type compound ( Rs)- 4 showed the best results in terms of both yield and diastereoselectivity. As a result of optimization of the reaction, the selectivity was improved up to 92:8 dr, and stereochemistry of the newly formed sulfur stereogenic center was revealed as ( Ss)-configuration.