1. Alkyne Insertion Enabled Vinyl to Acyl 1,5‐Palladium Migration: Rapid Access to Substituted 5‐Membered‐Dihydrobenzofurans and Indolines.
- Author
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Ding, Mingruo, Ou, Pengcheng, Li, Xuening, Yu, Yinghua, Niu, Mengmeng, Yang, Yongjian, Huang, Yewei, Wang, Zhi‐Xiang, and Huang, Xueliang
- Subjects
ACYL group ,VINYL polymers ,VINYLATION ,PALLADIUM ,INDOLINE ,ALLYLIC amination - Abstract
"Through space" palladium/hydrogen shift is an efficient strategy to achieve selective functionalization of a specific remote C−H bond. Compared with relatively extensive exploited 1,4‐palladium migration process, the relevant 1,5‐Pd/H shift was far less investigated. We herein report a novel 1,5‐Pd/H shift pattern between a vinyl and an acyl group. Through the pattern, rapid access to 5‐membered‐dihydrobenzofuran and indoline derivatives has been achieved. Further studies have unveiled an unprecedented trifunctionalization (vinylation, alkynylation and amination) of a phenyl ring through 1,5‐palladium migration relayed decarbonylative Catellani type reaction. A series of mechanistic investigations and DFT calculations have provided insights into the reaction pathway. Notably, it was unveiled that the 1,5‐palladium migration in our case prefers a stepwise mechanism involving a PdIV intermediate. [ABSTRACT FROM AUTHOR]
- Published
- 2023
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