Combined C-H functionalization/Cope rearrangement with vinyl ethers as a surrogate for the vinylogous Mukaiyama aldol reaction.

Combined C-H functionalization/Cope rearrangement with vinyl ethers as a surrogate for the vinylogous Mukaiyama aldol reaction.
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DOI:
10.1021/ja2051155
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发表时间:
2011-08-10
影响因子:
15
通讯作者:
Davies, Huw M. L.
Davies, Huw M. L.
中科院分区:
化学1区
文献类型:
--
作者:
Lian, Yajing;Davies, Huw M. L.

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乙烯基醚通过s-cis/boat转变选择性地经历组合的C-H官能化/科普重排反应(CHCR)。使用手性铑催化剂,产物以高度非对映选择性和对映选择性的方式产生。该反应可以被认为是传统的乙烯基-Mukaiyama羟醛缩合反应的替代物。已实现有效的动力学拆分,导致高对映体纯度的具有轴向手性的环状乙烯基醚的回收。
Vinyl ethers selectively undergo the combined C—H functionalization/Cope rearrangement reaction (CHCR) via an s-cis/boat transition. With chiral dirhodium catalysts, products are generated in a highly diastereoselective and enantioselective fashion. This reaction can be considered as a surrogate to the traditional vinylogous Mukaiyama aldol reaction. Effective kinetic resolution has been achieved, leading to the recovery of a cyclic vinyl ether with axial chirality of high enantiomeric purity.
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