A facile synthesis of α,β-unsaturated imines via palladium-catalyzed dehydrogenation

Chunyang Zhao, Rongwan Gao, Wenxuan Ma, Miao Li, Yifei Li, Qian Zhang, Wei Guan () and Junkai Fu ()
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Chunyang Zhao: Northeast Normal University
Rongwan Gao: Northeast Normal University
Wenxuan Ma: Northeast Normal University
Miao Li: Northeast Normal University
Yifei Li: Northeast Normal University
Qian Zhang: Northeast Normal University
Wei Guan: Northeast Normal University
Junkai Fu: Northeast Normal University

Nature Communications, 2024, vol. 15, issue 1, 1-12

Abstract: Abstract The dehydrogenation adjacent to an electron-withdrawing group provides an efficient access to α,β-unsaturated compounds that serving as versatile synthons in organic chemistry. However, the α,β-desaturation of aliphatic imines has hitherto proven to be challenging due to easy hydrolysis and preferential dimerization. Herein, by employing a pre-fluorination and palladium-catalyzed dehydrogenation reaction sequence, the abundant simple aliphatic amides are amendable to the rapid construction of complex molecular architectures to produce α,β-unsaturated imines. Mechanistic investigations reveal a Pd(0)/Pd(II) catalytic cycle involving oxidative H–F elimination of N-fluoroamide followed by a smooth α,β-desaturation of the in-situ generated aliphatic imine intermediate. This protocol exhibits excellent functional group tolerance, and even the carbonyl groups are compatible without any competing dehydrogenation, allowing for late-stage functionalization of complex bioactive molecules. The synthetic utility of this transformation has been further demonstrated by a diversity-oriented derivatization and a concise formal synthesis of (±)-alloyohimbane.

Date: 2024
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DOI: 10.1038/s41467-024-48737-9

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