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Synlett 2025; 36(18): 3000-3011
DOI: 10.1055/a-2630-1454
DOI: 10.1055/a-2630-1454
Account
Catalytic C–C Bond Formation via Aromatic C–H Bond Cleavage Using Low-Valent Iron-Phosphine Complexes
Authors
Supported by: Core Research for Evolutional Science and Technology JPMJSP2123
Abstract
This article presents our findings on catalytic ortho-selective C–C bond formations through the cleavage of C–H bonds in aromatic ketones using low-valent iron-phosphine complexes. We describe four types of catalytic transformations that convert C–H bonds into C–C bonds. Reactions involving terminal alkenes, such as vinyl and allylsilanes, aliphatic alkenes, styrenes, vinyl ethers, and enamines, yield the corresponding linear alkylation products. The coupling reaction using methylenecyclopropanes yields homoallylation products via alkene 1,2-insertion, followed by β-carbon elimination. The C–H alkenylation can be achieved by the reaction with internal alkynes. The use of 1,n-enynes (where n = 6, 7) as coupling partners for the C–H bond led to hydroarylative enyne cyclization products. The results of deuterium-labeling experiments of these reactions are also discussed.
Keywords
Low-valent iron-phosphine complex - C–H activation - C–C bond formation - Aromatic ketone - Alkenes - Alkynes - 1,n-EnynesPublication History
Received: 30 April 2025
Accepted after revision: 06 June 2025
Article published online:
24 July 2025
© 2025. Thieme. All rights reserved.
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