Iridium-catalyzed enantioselective allylic substitution of unstabilized enolates derived from α,β-unsaturated ketones.

Iridium-catalyzed enantioselective allylic substitution of unstabilized enolates derived from α,β-unsaturated ketones.
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虹膜催化的对映选择性烯丙基取代,源自α,β-不饱和酮的未稳定烯醇。

DOI:
10.1002/anie.201403844
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发表时间:
2014-08-11
影响因子:
16.6
通讯作者:
Hartwig, John F.
Hartwig, John F.
中科院分区:
化学1区
文献类型:
--
作者:
Chen, Ming;Hartwig, John F.

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我们报告了源自α,β,β-催化性的,对启发的silyl的侵蚀性替代反应,源自α,β-无饱和酮的非对称性shere液。抗癌剂的简短合成TEI-9826。
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 anti-cancer agent TEI-9826.
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