Stereochemistry and Mechanistic Study of Intramolecular Pd<sup>II</sup>‐Catalyzed Oxypalladation and 1,3‐Chirality‐Transfer Reactions

Abstract

<jats:title>Abstract</jats:title><jats:p>Pd<jats:sup>II</jats:sup>‐catalyzed cyclizations of chiral ε‐, ζ‐, and η‐hydroxy‐α,β‐unsaturated alcohols are described. The reactions took place stereospecifically to give chiral 2,5‐disubstituted tetrahydrofurans, 2,6‐disubstituted tetrahydropyrans, and 2,7‐disubstituted oxepanes, respectively. The chirality of the carbon center of the chiral allylic alcohol is transferred stereospecifically to the carbon center of the newly generated oxacyclic ring. A plausible reaction mechanism involves 1) chiral‐allylic‐alcohol‐induced <jats:italic>syn</jats:italic> facioselective formation of a Pd π‐complex, 2) <jats:italic>syn</jats:italic> oxypalladation, and 3) <jats:italic>syn</jats:italic> elimination of PdCl(OH), which provide a rational account for the stereochemical results.</jats:p>

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