Rh(I)催化C─C键活化对映选择性合成ε-内酰胺。

IF 16.9 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Shiyuan Sui,Hao Wu,Yuanyuan Guo,Gongming Chen,Junbiao Chang,Dachang Bai
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引用次数: 0

摘要

ε-内酰胺是药物化学中重要的结构基序,但如何在不产生副产物的情况下完全对映选择性地合成ε-内酰胺是一个挑战,已经引起了人们的极大兴趣。本文报道了通过Rh(I)催化氨基环丙烷的对映选择性C─C键活化,原子和步经济合成手性ε-内酰胺的方法。催化C─C键活化使手性红代环丁烷的定向生成绕过β-氢化物分解。随后烯烃单元的对映选择性环加成和裂解生成手性ε-内酰胺。得到了一系列富含对映体的ε-内酰胺,它们具有优异的区域和对映体选择性,可以进行多次立体定向转化。理论计算揭示了反应机理和对映体选择性控制的来源。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Enantioselective Synthesis of ε-Lactams via Rh(I)-Catalyzed C─C Bond Activation.
ε-Lactams are important structural motifs in medicinal chemistry, but a fully enantioselective synthesis without byproduct formation represents a challenge that has attracted significant research interest. Herein, we report an atom- and step-economic synthesis of chiral ε-lactams via Rh(I)-catalyzed enantioselective C─C bond activation of aminocyclopropanes. The catalytic C─C bond activation enables a directed generation of chiral rhodacyclobutanes that circumvents β-hydride decomposition. Subsequent enantioselective cycloaddition of the alkene unit and then fragmentation generates chiral ε-lactams. A range of enantioenriched ε-lactams have been obtained with excellent regio- and enantioselectivities, which can undergo several stereospecific transformations. Theoretical calculations are performed to reveal the reaction mechanism and the origin of enantioselectivity control.
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来源期刊
CiteScore
26.60
自引率
6.60%
发文量
3549
审稿时长
1.5 months
期刊介绍: Angewandte Chemie, a journal of the German Chemical Society (GDCh), maintains a leading position among scholarly journals in general chemistry with an impressive Impact Factor of 16.6 (2022 Journal Citation Reports, Clarivate, 2023). Published weekly in a reader-friendly format, it features new articles almost every day. Established in 1887, Angewandte Chemie is a prominent chemistry journal, offering a dynamic blend of Review-type articles, Highlights, Communications, and Research Articles on a weekly basis, making it unique in the field.
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