Divergent rhodium-catalyzed electrochemical vinylic C–H annulation of acrylamides with alkynes

Yi-Kang Xing, Xin-Ran Chen, Qi-Liang Yang, Shuo-Qing Zhang, Hai-Ming Guo, Xin Hong () and Tian-Sheng Mei ()
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Yi-Kang Xing: Chinese Academy of Sciences
Xin-Ran Chen: Zhejiang University
Qi-Liang Yang: Henan Normal University
Shuo-Qing Zhang: Zhejiang University
Hai-Ming Guo: Henan Normal University
Xin Hong: Zhejiang University
Tian-Sheng Mei: Chinese Academy of Sciences

Nature Communications, 2021, vol. 12, issue 1, 1-9

Abstract: Abstract α-Pyridones and α-pyrones are ubiquitous structural motifs found in natural products and biologically active small molecules. Here, we report an Rh-catalyzed electrochemical vinylic C–H annulation of acrylamides with alkynes, affording cyclic products in good to excellent yield. Divergent syntheses of α-pyridones and cyclic imidates are accomplished by employing N-phenyl acrylamides and N-tosyl acrylamides as substrates, respectively. Additionally, excellent regioselectivities are achieved when using unsymmetrical alkynes. This electrochemical process is environmentally benign compared to traditional transition metal-catalyzed C–H annulations because it avoids the use of stoichiometric metal oxidants. DFT calculations elucidated the reaction mechanism and origins of substituent-controlled chemoselectivity. The sequential C–H activation and alkyne insertion under rhodium catalysis leads to the seven-membered ring vinyl-rhodium intermediate. This intermediate undergoes either the classic neutral concerted reductive elimination to produce α-pyridones, or the ionic stepwise pathway to produce cyclic imidates.

Date: 2021
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DOI: 10.1038/s41467-021-21190-8

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