Enantioselective Cyanosilylation of Ketones with Lithium(I) Dicyanotrimethylsilicate(IV) Catalyzed by a Chiral Lithium(I) Phosphoryl Phenoxide
Enantioselective Cyanosilylation of Ketones with Lithium(I) Dicyanotrimethylsilicate(IV) Catalyzed by a Chiral Lithium(I) Phosphoryl Phenoxide
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DOI：
10.1002/anie.201510682
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发表时间：
2016-03-14
影响因子：
16.6
通讯作者：
Ishihara, Kazuaki
中科院分区：
文献类型：
--
作者：
Hatano, Manabu;Yamakawa, Katsuya;Ishihara, Kazuaki
通过使用手性磷酰基苯氧基锂(I)水配合物作为酸/碱协同催化剂，开发了酮的高度对映选择性氰基甲硅烷基化。 Me3SiCN/LiCN 原位生成的五配位硅酸盐是一种极其活泼的氰基试剂。描述了 30 克规模的反应以及 (+)-13-羟基异环鲸蜡的关键前体的合成。
A highly enantioselective cyanosilylation of ketones was developed by using a chiral lithium(I) phosphoryl phenoxide aqua complex as an acid/base cooperative catalyst. The pentacoordinate silicate generated insitu from Me3SiCN/LiCN acts as an extremely reactive cyano reagent. Described is a 30gram scale reaction and the synthesis of the key precursor to (+)-13-hydroxyisocyclocelabenzine.