Palladium-Catalyzed Diastereoselective Synthesis of (Z)-Conjugated Enynyl Homoallylic Alcohols

The diastereoselective synthesis of anti-homoallylic alcohols bearing conjugated (Z)-enynes through a palladium-catalyzed three-component reaction is described. This reaction features a broad substrate scope, good functional group compatibility, and high levels of (Z)-alkene stereocontrol. In this reaction, Pd(0) functions as a catalyst in two fundamental steps of the tandem sequence: 1) the generation of a borylated pi-allylpalladium species from bifunctional conjunctive reagents, inducing umpolung allylation of aldehydes, and 2) C(sp(2))-C(sp) cross-coupling. Further transformations of the obtained products highlight their synthetic utility.

Automated summary

The diastereoselective synthesis of anti-homoallylic alcohols bearing conjugated (Z)-enynes through a palladium-catalyzed three-component reaction is described, featuring a broad substrate scope, good functional group compatibility, and high levels of (Z)-alkene stereocontrol. The reaction involves Pd(0) functioning as a catalyst in two fundamental steps: the generation of a borylated pi-allylpalladium species inducing umpolung allylation of aldehydes, and C(sp(2))-C(sp) cross-coupling. Further transformations of the obtained products highlight their synthetic utility.