Synthesis of Allenes by Hydroalkylation of 1,3-Enynes with Ketones Enabled by Cooperative Catalysis

A method for the synthesis of allenes by the addition of ketones to 1,3-enynes by cooperative Pd(0)Senphos/B(C6F5)3/NR3 catalysis is described. A wide range of aryl- and aliphatic ketones undergo addition to various 1,3-enynes in high yields at room temperature. Mechanistic investigations revealed...

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Bibliographic Details
Published in:	Journal of the American Chemical Society Vol. 145; no. 39; pp. 21638 - 21645
Main Authors:	Eaton, Maxwell, Dai, Yuping, Wang, Ziyong, Li, Bo, Lamine, Walid, Miqueu, Karinne, Liu, Shih-Yuan
Format:	Journal Article
Language:	English
Published:	United States American Chemical Society 04-10-2023
Subjects:	Chemical Sciences or physical chemistry Theoretical and Allenes Palladium Catalysts Ketones Reaction mechanisms
Online Access:	Get full text
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Summary:	A method for the synthesis of allenes by the addition of ketones to 1,3-enynes by cooperative Pd(0)Senphos/B(C6F5)3/NR3 catalysis is described. A wide range of aryl- and aliphatic ketones undergo addition to various 1,3-enynes in high yields at room temperature. Mechanistic investigations revealed a rate-determining outer-sphere proton transfer mechanism, which was corroborated by DFT calculations.
Bibliography:	ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 M.E. performed the experimental synthetic and mechanistic work guided by S.-Y.L. Y.D. performed the computational work guided by K.M. Z.W. discovered the title reaction and performed preliminary reaction optimization. B.L. solved the X-ray structures. W.L. provided initial computational analysis. The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. Author Contributions
ISSN:	0002-7863 1520-5126 1520-5126
DOI:	10.1021/jacs.3c08151