The one-pot synthesis of B,y-unsaturated ketones bearing all-carbon quaternary centers at the oc-position via a highly regioselective hydroacylation of alienes using acyl chlorides and aluminum hydride is reported. The Cu-catalyzed hydroalumination of 1,1-disubstituted and 1,1,3-trisubstituted alienes with dii-sobutylaluminum hydride resulted in allylaluminum reagents that underwent regioselective acylation in the presence of acid chlorides. Various derivatives of alienes and acyl chlorides were compatible with this process, and a-quaternary ketones were obtained in high yields with excellent regioselectivity.
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