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Highly diastereoselective construction of acyclic systems with two adjacent quaternary stereocenters by allylation of ketones.

Unsymmetrical ketones and allyltitanocenes generated by the desulfurizative titanation of γ,γ-disubstituted allyl phenyl sulfides react under highly diastereoselective construction of adjacent quaternary stereocenters (see scheme; R(L) = large group, R(S) = small group). The title reaction is stereospecific: the anti- and syn-homoallylic alcohols are obtained by the reaction of E- and Z-allylic sulfides, respectively.