Pd-Catalyzed γ‑Acetoxylation of Alkylamides: Structural Influence of Directing Groups

Although direct acetoxylation and cyclization of alkylamide have been extensively reported, investigation of the structural influence of directing groups on selectivity is limited. Pd-catalyzed 2-methoxyiminoacyl (MIA) assisted γ-acetoxylation of alkylamides has been developed. Further DFT studies h...

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Published inJournal of organic chemistry Vol. 87; no. 9; pp. 6378 - 6386
Main Authors Liu, Peng-Yu, Zhao, Shi-Chen, Zhang, Ming-Yuan, Song, Lijuan, Wang, Caiping, Yu, Fang, Meng, Qingtao, Zhang, Zhiqiang, He, Yu-Peng
Format Journal Article
LanguageEnglish
Published United States American Chemical Society 06.05.2022
Subjects
group effect
organic chemistry
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Summary:Although direct acetoxylation and cyclization of alkylamide have been extensively reported, investigation of the structural influence of directing groups on selectivity is limited. Pd-catalyzed 2-methoxyiminoacyl (MIA) assisted γ-acetoxylation of alkylamides has been developed. Further DFT studies have demonstrated that the directing groups have a significant influence on the reductive elimination step. The strong electron-donating effect of the OMe group in MIA leads to the preferential formation of a five-membered cyclopalladium (OAc–Pd-C) complex, which favors the acetoxylation pathway.
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content type line 23
ISSN:0022-3263
1520-6904
1520-6904
DOI:10.1021/acs.joc.2c00085