Photoinduced Five-Component Radical Relay Aminocarbonylation of Alkenes

Radical single carbonylation reactions with CO constitute a direct and robust strategy toward various carbonyl compounds from readily available chemicals, and have been extensively studied over the past decades. However, realizing highly selective catalytic systems for controlled radical double carb...

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Published inAngewandte Chemie International Edition Vol. 62; no. 41; p. e202309460
Main Authors Lu, Bin, Zhang, Zhihan, Jiang, Min, Liang, Dong, He, Zi-Wei, Bao, Feng-Shuo, Xiao, Wen-Jing, Chen, Jia-Rong
Format Journal Article
LanguageEnglish
Published WEINHEIM Wiley 09.10.2023
Wiley Subscription Services, Inc
EditionInternational ed. in English
Subjects
Alkenes
Carbonyl compounds
Carbonyls
Cations
Chemistry
Chemistry, Multidisciplinary
Cross coupling
Nitrogen radicals
Physical Sciences
Radicals
Relay
Science & Technology
Alkenes
CATALYZED DOUBLE CARBONYLATION
Carbon Monoxide
Multicomponent Reaction
COMPLEXES
ATOM-TRANSFER CARBONYLATION
REACTIVITY
ALKYL IODIDES
Reaction Mechanisms
CARBON-MONOXIDE
AMINES
Visible Light
ARYL HALIDES
CHEMISTRY
C-H TRIFLUOROMETHYLATION
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Summary:Radical single carbonylation reactions with CO constitute a direct and robust strategy toward various carbonyl compounds from readily available chemicals, and have been extensively studied over the past decades. However, realizing highly selective catalytic systems for controlled radical double carbonylation reactions has remained a substantial challenge, particularly for the more advanced multicomponent variants, despite their great potential value. Herein, we report a visible-light-driven radical relay five-component radical double aminocarbonylation reaction of unactivated alkenes using CO under metal-free conditions. This protocol provides direct access to valuable & gamma;-trifluoromethyl & alpha;-ketoamides with good yields and high chemoselectivity. Crucial was the identification of distinct dual roles of amine coupling partners, sequentially acting as electron donors for the formation of photoactive electron donor-acceptor (EDA) complexes with radical precursors and then as a CO acceptor via nitrogen radical cations to form carbamoyl radicals. Cross-coupling of carbamoyl radicals with the acyl radicals that are formed in an alkene-based relay process affords double aminocarbonylation products. A visible-light-driven radical relay five-component double aminocarbonylation reaction of alkenes is described for direct access to valuable & gamma;-trifluoromethyl & alpha;-ketoamides with good yields and selectivities. Crucial was the identification of distinct dual roles of the amine coupling partners, which sequentially act as electron donors for the formation of photoactive electron donor-acceptor complexes with radical precursors and then as a CO acceptor to form carbamoyl radicals.image
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ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202309460