Catalytic asymmetric vinylation of ketones
Catalytic asymmetric vinylation of ketones
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DOI：
10.1021/ja049206g
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发表时间：
2004-06-02
影响因子：
15
通讯作者：
Walsh, PJ
中科院分区：
文献类型：
--
作者：
Li, HM;Walsh, PJ
本通讯描述了乙烯基锌试剂对芳香族、α，β-不饱和和二烷基酮的催化不对称1，2-加成反应，对映选择性在79 - 97%之间，产率在84 - 98%之间。这些反应的产物是具有手性季中心的叔烯丙醇，其在有机合成中是有用的。该反应包括在手性钛基刘易斯酸催化剂的存在下，末端炔的锆氢化，金属转移到锌，和加成到酮。反应在室温下24 h内顺利进行。
This communication describes the catalytic asymmetric 1,2-addition of vinylzinc reagents to aromatic, α,β-unsaturated, and dialkyl ketones with enantioselectivities between 79 and 97% and with yields ranging from 84 to 98%. The products of these reactions are tertiary allylic alcohols with chiral quaternary centers that are useful in organic synthesis. The reaction involves hydrozirconation of a terminal alkyne, transmetalation to zinc, and addition to a ketone in the presence of a chiral titanium-based Lewis acid catalyst. The reactions proceed smoothly at room temperature in under 24 h.