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用于构建N-C轴手性的对映选择性钯电催化C-H烯烃化和烯丙基化反应

Enantioselective palladaelectro-catalyzed C-H olefinations and allylations for N-C axial chirality.

作者信息

Dhawa Uttam, Wdowik Tomasz, Hou Xiaoyan, Yuan Binbin, Oliveira João C A, Ackermann Lutz

机构信息

Institut für Organische und Biomolekulare Chemie, Georg-August-Universität Göttingen Tammannstraße 2 37077 Göttingen Germany

Wöhler Research Institute for Sustainable Chemistry (WISCh), Georg-August-Universität Göttingen Tammannstraße 2 37077 Göttingen Germany.

出版信息

Chem Sci. 2021 Oct 13;12(42):14182-14188. doi: 10.1039/d1sc04687j. eCollection 2021 Nov 3.

DOI:10.1039/d1sc04687j
PMID:34760203
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC8565398/
Abstract

Enantioselective palladaelectro-catalyzed C-H alkenylations and allylations were achieved with easily-accessible amino acids as transient directing groups. This strategy provided access to highly enantiomerically-enriched N-C axially chiral scaffolds under exceedingly mild conditions. The synthetic utility of our strategy was demonstrated by a variety of alkenes, while the versatility of our approach was reflected by atroposelective C-H allylations. Computational studies provided insights into a facile C-H activation by a seven-membered palladacycle.

摘要

利用易于获得的氨基酸作为瞬态导向基团,实现了对映选择性钯电催化的C-H烯基化和烯丙基化反应。该策略在极为温和的条件下提供了获得高度对映体富集的N-C轴手性骨架的途径。各种烯烃证明了我们策略的合成实用性,而通过非对映选择性C-H烯丙基化反应体现了我们方法的通用性。计算研究为七元钯环实现的简便C-H活化提供了见解。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1d3b/8565398/e6ea58e6fd9a/d1sc04687j-s5.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1d3b/8565398/e6ea58e6fd9a/d1sc04687j-s5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1d3b/8565398/d0a2c51e9518/d1sc04687j-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1d3b/8565398/abe69d7b121f/d1sc04687j-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1d3b/8565398/18f0ff3606c7/d1sc04687j-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1d3b/8565398/746fdc736d0f/d1sc04687j-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1d3b/8565398/ff7eaa9eec42/d1sc04687j-f3.jpg
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