Additive Tuned Selective Synthesis of Bicyclo[3.3.0]octan-1-ols and Bicyclo[3.1.0]hexan-1-ols Mediated by AllylSmBr

The selective construction of bicyclo[3.3.0]­octan-1-ols and bicyclo[3.1.0]­hexan-1-ols was achieved by using an allylSmBr/additive(s) system. By employing HMPA as the only additive, the momoallylation/ketone–alkene coupling occurred preferably and afforded bicyclo[3.3.0]­octan-1-ols in good yields with high diastereoselectivities. While the ester–alkene coupling predominated to generate bicyclo[3.1.0]­hexan-1-ols in moderate yields with excellent diastereoselectivities in the presence of a proton source, such as pyrrole as the coadditive with HMPA. The tunable reactivity of allylSmBr by additive(s) would make it a versatile reagent in organic synthesis.