Regio- and Stereoselective Ni-Catalyzed 1,4-Hydroboration of 1,3-Dienes: Access to Stereodefined (Z)-Allylboron Reagents and Derived Allylic Alcohols

A catalytic regio- and stereoselective 1,4-hydroboration of 1,3-dienes was accomplished with pinacolborane in the presence of Ni(cod)(2) and PCy(3). This reaction exhibits broad substrate scope operating on a range of substituted dienes and occurs with generally high levels of selectivity and efficiency. Reactivity patterns suggest that the reactive conformation of the diene is the S-cis form. The intermediate allylboronate can be oxidized to stereodefined allylic alcohols or can be used in stereoselective carbonyl addition reactions.