Stereoselective Formation of Fully Substituted Ketone Enolates
Stereoselective Formation of Fully Substituted Ketone Enolates
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DOI：
10.1002/anie.201601883
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发表时间：
2016-04-25
影响因子：
16.6
通讯作者：
Marek, Ilan
中科院分区：
文献类型：
--
作者：
Haimov, Elvira;Nairoukh, Zackaria;Marek, Ilan
立体化学定义的无环全取代烯醇化酮在季碳立体中心的不对称合成中具有重要的应用价值。在此，我们描述了一种方法，导致几个新的立体中心的形成，通过一个组合的羰基-氨基甲酰基转移的金属化加成，揭示原位立体定义的α，α-二取代烯醇化酮作为一个单一的立体异构体。该方法可以从烯醇氨基甲酸酯得到一系列具有良好非对映异构体比例的羟醛和曼尼希产物。
The application of stereochemically defined acyclic fully substituted enolates of ketones to the enantioselective synthesis of quaternary carbon stereocenters would be highly valuable. Herein, we describe an approach leading to the formation of several new stereogenic centers through a combined metalation-addition of a carbonyl-carbamoyl transfer to reveal insitu stereodefined alpha,alpha-disubstituted enolates of ketone as a single stereoisomer. This approach could produce a series of aldol and Mannich products from enol carbamate with excellent diastereomeric ratios.