铱催化由α,β-不饱和酮衍生的不稳定烯醇盐的对映选择性烯丙基取代反应。
Iridium-catalyzed enantioselective allylic substitution of unstabilized enolates derived from α,β-unsaturated ketones.
作者信息
Chen Ming, Hartwig John F
机构信息
Department of Chemistry, University of California, Berkeley, CA 94720 (USA).
出版信息
Angew Chem Int Ed Engl. 2014 Aug 11;53(33):8691-5. doi: 10.1002/anie.201403844. Epub 2014 Jun 10.
Abstract
We report Ir-catalyzed, enantioselective allylic substitution reactions of unstabilized silyl enolates derived from α,β-unsaturated ketones. Asymmetric allylic substitution of a variety of allylic carbonates with silyl enolates gave allylated products in 62-94% yield with 90-98% ee and >20:1 branched-to-linear selectivity. The synthetic utility of this method was illustrated by the short synthesis of an anticancer agent, TEI-9826.
摘要
我们报道了由α,β-不饱和酮衍生的不稳定硅基烯醇化物的铱催化对映选择性烯丙基取代反应。各种烯丙基碳酸酯与硅基烯醇化物的不对称烯丙基取代反应得到了烯丙基化产物，产率为62-94%，对映体过量值为90-98%，支链与直链选择性大于20:1。一种抗癌药物TEI-9826的简短合成证明了该方法的合成实用性。
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