Bimetallic Rhodium(II)/Indium(III) Relay Catalysis for Tandem Insertion/Asymmetric Claisen Rearrangement
Bimetallic Rhodium(II)/Indium(III) Relay Catalysis for Tandem Insertion/Asymmetric Claisen Rearrangement
复制标题
双金属铑(II)/铟(III)中继催化串联插入/不对称克莱森重排
DOI：
10.1002/anie.201810410
复制
发表时间：
2018-12-10
影响因子：
16.6
通讯作者：
Feng, Xiaoming
中科院分区：
文献类型：
--
作者：
Chen, Yushuang;Dong, Shunxi;Feng, Xiaoming
N-磺酰基-1,2,3-三唑与烯丙醇酯的催化插入/不对称克莱森重排串联反应的第一个例子是通过涉及非手性铑盐和手性N,N'-二氧化铟(III)络合物的双金属接力催化系统实现的。这种歧管可以克服单一Rh-II催化的局限性，为各种对映体富集的β/γ-氨基酸衍生物提供直接、简便的途径，产率高达99%，具有优异的非对映和对映选择性（高达>95:5 dr，98:2 er）。此外，基于催化剂的控制实验和X射线晶体结构，提出了可能的过渡态模型来阐明手性诱导的起源。
The first example of catalytic insertion/asymmetric Claisen rearrangement tandem reaction of N-sulfonyl-1,2,3-triazoles with allyl alcohol esters was achieved by bimetallic relay catalytic systems involving achiral rhodium salt and chiral N,N'-dioxide-indium(III) complex. This manifold could overcome the limitation of single Rh-II catalysis, providing a straight and facile route to various enantioenriched beta/gamma-amino acid derivatives in high yields (up to 99%) with excellent diastereo- and enantioselectivities (up to >95:5 dr, 98:2 er). Moreover, possible transition state models were proposed to elucidate the origin of chiral induction based on the control experiments and X-ray crystal structure of the catalyst.