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芳基环金物种与芳基硼酸的化学计量反应性与催化反应性：深入了解金催化的氧化C(sp)-H芳基化反应机理

Stoichiometric to catalytic reactivity of the aryl cycloaurated species with arylboronic acids: insight into the mechanism of gold-catalyzed oxidative C(sp)-H arylation.

作者信息

Wu Qian, Du Chenglong, Huang Yumin, Liu Xingyan, Long Zhen, Song Feijie, You Jingsong

机构信息

Key Laboratory of Green Chemistry and Technology of Ministry of Education , College of Chemistry and State Key Laboratory of Biotherapy , West China Medical School , Sichuan University , 29 Wangjiang Road , Chengdu 610064 , PR China . Email:

出版信息

Chem Sci. 2015 Jan 1;6(1):288-293. doi: 10.1039/c4sc02070g. Epub 2014 Oct 9.

DOI:10.1039/c4sc02070g
PMID:28626549
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC5463920/
Abstract

Based on the well-defined five-membered aryl gold(iii) complexes, [Au(tpy)X] ( and ) and [AuBr(Ph)(tpy)] (), as well as the aryl gold(iii) complex [AuCl(Ph)(tpy)] () (tpy = 2-(-tolyl)pyridine) as reliable models, we present a detailed study of the mechanism for gold(iii)-catalyzed oxidative cross-coupling reactions between cycloaurable arenes and arylboronic acids. Here we report the direct evidence for a mechanistic proposal including arene C-H activation, transmetallation and biaryl reductive elimination. The chelation-assisted C-H activation strategy has been used for the development of the gold(iii)-catalyzed C-H bond arylation of arenes with aryl reagents to forge extended π-conjugated systems.

摘要

基于结构明确的五元芳基金（III）配合物，即[Au(tpy)X]（ 和 ）、[AuBr(Ph)(tpy)]（ ）以及芳基金（III）配合物[AuCl(Ph)(tpy)]（ ）（tpy = 2 -（-甲苯基）吡啶）作为可靠模型，我们对金（III）催化的可环金属化芳烃与芳基硼酸之间的氧化交叉偶联反应机理进行了详细研究。在此，我们报告了一个机理提议的直接证据，该提议包括芳烃C-H活化、转金属化和联芳基还原消除。螯合辅助的C-H活化策略已被用于开发金（III）催化的芳烃与芳基试剂的C-H键芳基化反应，以构建扩展的π共轭体系。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/062c/5463920/6a0876f307f8/c4sc02070g-s3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/062c/5463920/c1545c1c5f42/c4sc02070g-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/062c/5463920/b96ed733dcfc/c4sc02070g-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/062c/5463920/96580c5463d5/c4sc02070g-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/062c/5463920/23ef3c2afa85/c4sc02070g-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/062c/5463920/df7bd1ddd683/c4sc02070g-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/062c/5463920/6a0876f307f8/c4sc02070g-s3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/062c/5463920/c1545c1c5f42/c4sc02070g-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/062c/5463920/b96ed733dcfc/c4sc02070g-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/062c/5463920/96580c5463d5/c4sc02070g-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/062c/5463920/23ef3c2afa85/c4sc02070g-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/062c/5463920/df7bd1ddd683/c4sc02070g-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/062c/5463920/6a0876f307f8/c4sc02070g-s3.jpg

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