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无预活化条件下铑（I）催化的嗪的基控完全选择性 C-H 邻位烷基化反应。

Base-Controlled Completely Selective Linear or Branched Rhodium(I)-Catalyzed C-H ortho-Alkylation of Azines without Preactivation.

机构信息

Department of Chemistry, Yale University, 225 Prospect St., New Haven, CT, 06520, USA.

Pfizer, Inc., Medicinal Sciences, Groton, CT, 06340, USA.

出版信息

Angew Chem Int Ed Engl. 2017 May 15;56(21):5899-5903. doi: 10.1002/anie.201702409. Epub 2017 Apr 21.

DOI:10.1002/anie.201702409
PMID:28429455
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC5558092/
Abstract

A [Rh ]/bisphosphine/base catalytic system for the ortho-selective C-H alkylation of azines by acrylates and acrylamides is reported. This catalytic system features an unprecedented complete linear or branched selectivity that is solely dependent on the catalytic base that is used. Complete branched selectivity is even achieved for ethyl methacrylate, which enables the introduction of a quaternary carbon center. Excellent functional group compatibility is demonstrated for both linear and branched alkylations. The operational simplicity and broad scope of this transformation allow for rapid access to functionalized azines of direct pharmaceutical and agrochemical relevance.

摘要

报道了一种 [Rh ]/双膦/堿催化体系，用于通过丙烯酸酯和丙烯酰胺对嗪进行邻位选择性 C-H 烷基化。该催化体系具有前所未有的完全线性或支化选择性，仅取决于所用的催化堿。甚至对于甲基丙烯酸乙酯也实现了完全的支化选择性，从而能够引入季碳原子。该反应对线性和支化烷基化都具有很好的官能团兼容性。该转化操作简单，适用范围广泛，可快速获得具有直接药物和农用化学品相关性的功能化嗪。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/25eb/5558092/7ca87507fa9e/nihms894915f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/25eb/5558092/8ad727f26175/nihms894915f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/25eb/5558092/9834c14a9e7f/nihms894915f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/25eb/5558092/b177fe4b6cbf/nihms894915f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/25eb/5558092/abb5bd6e4471/nihms894915f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/25eb/5558092/7ca87507fa9e/nihms894915f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/25eb/5558092/8ad727f26175/nihms894915f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/25eb/5558092/9834c14a9e7f/nihms894915f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/25eb/5558092/b177fe4b6cbf/nihms894915f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/25eb/5558092/abb5bd6e4471/nihms894915f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/25eb/5558092/7ca87507fa9e/nihms894915f5.jpg

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