Regio- and enantioselective control in the reactions of alpha-(N-carbamoyl)alkylcuprates with allylic phosphates.
Regio- and enantioselective control in the reactions of alpha-(N-carbamoyl)alkylcuprates with allylic phosphates.
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DOI：
10.1021/ol0364576
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发表时间：
2004-02
期刊：
影响因子：
5.2
通讯作者：
R. Dieter;V. Gore;Ningyi Chen
中科院分区：
文献类型：
--
作者：
R. Dieter;V. Gore;Ningyi Chen
α-（N-氨基甲酰基）烷基铜酸酯（RCuCNLi或R2 CuLi）与烯丙基磷酸酯反应以良好的化学产率得到高烯丙基胺。区域选择性由铜酸盐试剂和磷酸盐底物中的空间因素决定，并且可以设计系统以干净地产生S（N）2'或S（N）2取代产物。优异的对映体选择性可以用比例消旋α-二[（N-氨基甲酰基）烷基]铜酸盐和非手性磷酸盐或用比例消旋烯丙基磷酸盐和非手性铜酸盐试剂来实现。[反应：见正文]
Alpha-(N-carbamoyl)alkylcuprates (RCuCNLi or R2CuLi) react with allylic phosphates to afford homoallylic amines in good chemical yields. Regioselectivity is governed by steric factors in both the cuprate reagent and phosphate substrate and systems can be designed to give either the S(N)2' or S(N)2 substitution product cleanly. Excellent enantioselectivities can be achieved with either a scalemic alpha-di[(N-carbamoyl)alkyl]cuprate and an achiral phosphate or with a scalemic allylic phosphate and an achiral cuprate reagent. [reaction: see text]