External oxidant-compatible phosphorus(III)-directed site-selective C-H carbonylation

Ben Dong; Jiasheng Qian; Mingjie Li; Zheng-Jun Wang; Minyan Wang; Dingyi Wang; Chengkai Yuan; Ying Han; Yue Zhao; Zhuangzhi Shi

doi:10.1126/sciadv.abd1378

External oxidant-compatible phosphorus(III)-directed site-selective C-H carbonylation

Sci Adv. 2020 Dec 16;6(51):eabd1378. doi: 10.1126/sciadv.abd1378. Print 2020 Dec.

Authors

Ben Dong¹, Jiasheng Qian^{1

2}, Mingjie Li¹, Zheng-Jun Wang¹, Minyan Wang¹, Dingyi Wang¹, Chengkai Yuan¹, Ying Han¹, Yue Zhao¹, Zhuangzhi Shi³

Affiliations

¹ State Key Laboratory of Coordination Chemistry, Chemistry and Biomedicine Innovation Center (ChemBIC), School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093 (China).
² College of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002 (China).
³ State Key Laboratory of Coordination Chemistry, Chemistry and Biomedicine Innovation Center (ChemBIC), School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093 (China). shiz@nju.edu.cn.

Abstract

The first development of an external oxidant-compatible system involving a phosphorus(III)-directed C-H functionalization has been uncovered. An efficient C-H esterification of indoles with CO and alcohols has been reported in which the high reactivity and the exclusive C7-selectivity derives from the selection of a P(III)-directing group and the utilization of benzoquinone as an external oxidant with palladium catalysis. This strategy shows many advantages, involving an easily accessible and removable directing group, the use of cheap carbonylation sources, a broad substrate scope, and excellent positional selectivity. Two cyclopalladated intermediates were confirmed by x-ray analysis, uncovering key mechanistic features of this P(III)-directed C-H metalation event.

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