Stereoselective Formation of Trisubstituted (<i>Z</i>)‑Chloroalkenes Adjacent to a Tertiary Carbon Stereogenic Center by Organocuprate-Mediated Reduction/Alkylation

Abstract

A robust and efficient method for the synthesis of trisubstituted (<i>Z</i>)-chloroalkenes is described. A one-pot reaction of γ,γ-dichloro-α,β-enoyl sultams involving organocuprate-mediated reduction/asymmetric alkylation affords α-chiral (<i>Z</i>)-chloroalkene derivatives in moderate to high yields with excellent diastereoselectivity, and allylic alkylation of internal allylic <i>gem</i>-dichlorides is also demonstrated. This study provides the first examples of the use of allylic <i>gem</i>-dichlorides adjacent to the chiral center for novel 1,4-asymmetric induction