Department of Applied Chemistry, Graduate School of Engineering, Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588, Japan.
Angew Chem Int Ed Engl. 2012 Jul 16;51(29):7263-6. doi: 10.1002/anie.201202808. Epub 2012 Jun 8.
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.
不对称酮和烯丙基金属钛化合物由γ,γ-二取代烯丙基苯基硫醚的脱硫钛化反应生成，通过高度非对映选择性构建相邻的季立体中心（见方案；R(L) = 大基团，R(S) = 小基团）。标题反应具有立体特异性：E-和 Z-烯丙基硫醚反应分别得到反式和顺式同烯丙基醇。
