Divergent rhodium-catalyzed electrochemical vinylic C-H annulation of acrylamides with alkynes.
Nat Commun. 2021 02 10; 12(1):930.NC

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.

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Authors+Show Affiliations

Xing YK

State Key Laboratory of Organometallic Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai, China.

Chen XR

Department of Chemistry, Zhejiang University, Hangzhou, China.

Yang QL

Henan Key Laboratory of Organic Functional Molecules and Drug Innovation, Henan Normal University, Xinxiang, Henan, China.

Zhang SQ

Department of Chemistry, Zhejiang University, Hangzhou, China.

Guo HM

Henan Key Laboratory of Organic Functional Molecules and Drug Innovation, Henan Normal University, Xinxiang, Henan, China.

Hong X

Department of Chemistry, Zhejiang University, Hangzhou, China. hxchem@zju.edu.cn.

Mei TS

Pub Type(s)

Journal Article

Research Support, Non-U.S. Gov't

Language

eng

PubMed ID

33568643

Citation

Xing, Yi-Kang, et al. "Divergent Rhodium-catalyzed Electrochemical Vinylic C-H Annulation of Acrylamides With Alkynes." Nature Communications, vol. 12, no. 1, 2021, p. 930.

Xing YK, Chen XR, Yang QL, et al. Divergent rhodium-catalyzed electrochemical vinylic C-H annulation of acrylamides with alkynes. Nat Commun. 2021;12(1):930.

Xing, Y. K., Chen, X. R., Yang, Q. L., Zhang, S. Q., Guo, H. M., Hong, X., & Mei, T. S. (2021). Divergent rhodium-catalyzed electrochemical vinylic C-H annulation of acrylamides with alkynes. Nature Communications, 12(1), 930. https://doi.org/10.1038/s41467-021-21190-8

Xing YK, et al. Divergent Rhodium-catalyzed Electrochemical Vinylic C-H Annulation of Acrylamides With Alkynes. Nat Commun. 2021 02 10;12(1):930. PubMed PMID: 33568643.

* Article titles in AMA citation format should be in sentence-case

TY - JOUR T1 - Divergent rhodium-catalyzed electrochemical vinylic C-H annulation of acrylamides with alkynes. AU - Xing,Yi-Kang, AU - Chen,Xin-Ran, AU - Yang,Qi-Liang, AU - Zhang,Shuo-Qing, AU - Guo,Hai-Ming, AU - Hong,Xin, AU - Mei,Tian-Sheng, Y1 - 2021/02/10/ PY - 2020/10/14/received PY - 2021/01/14/accepted PY - 2021/2/11/entrez PY - 2021/2/12/pubmed PY - 2021/2/12/medline SP - 930 EP - 930 JF - Nature communications JO - Nat Commun VL - 12 IS - 1 N2 - 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. SN - 2041-1723 UR - https://www.unboundmedicine.com/medline/citation/33568643/Divergent_rhodium_catalyzed_electrochemical_vinylic_C_H_annulation_of_acrylamides_with_alkynes_ DB - PRIME DP - Unbound Medicine ER -

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Divergent rhodium-catalyzed electrochemical vinylic C-H annulation of acrylamides with alkynes.Nat Commun. 2021 02 10; 12(1):930.NC