Synthesis of Highly Functionalized Allylic Alcohols from Vinyl Oxiranes and N-Tosylhydrazones via a Tsuji-Trost-Like "Palladium-Iodide" Catalyzed Coupling.

An unprecedented efficient palladium(0)-catalyzed reaction of vinyl oxiranes with N-tosylhydrazones, affording "skipped" allylic alcohols in total regioselectivity and stereoselectivity, with excellent functional-group compatibility, is reported. In this Tsuji-Trost-like allylation, we propose the use of N-tosylhydrazones as a synthetic equivalent of α-styryl anions. More than 20 new products are described, including naturally occurring derivatives. A catalytic system involving an iodide (I-) source is necessary to sustain the catalytic cycle.