康 · 学术 | Reaction of the Day No. 1351

转自：康龙化成

Csp3−Csp2 Coupling of Isonitriles and (Hetero)arenes through a Photoredox-Catalyzed Double Decyanation Process

MaríaMartín, Rafael Martín Romero, Chiara Portolani, and Mariola Tortosa*

OrganicChemistry Department and Center for Innovation in Advanced Chemistry(ORFEO−CINQA), Universidad Autónoma de Madrid (UAM), 28049 Madrid, Spain;

Institutefor Advanced Research in Chemical Sciences (IAdChem), Universidad Autónoma de Madrid, Madrid 28049, Spain;

Departmentof Industrial Chemistry “Toso Montanari”, Alma Mater Studiorum−University of Bologna, 40129 Bologna, Italy;

—ACS Catal. 2024,14, 17286−17292

Recommended by Murong Xu_MC3

KEYWORDS: Photo Catalysis (反应类型),decyanation (反应类型), Isonitriles (原料),aryl nitrile (原料),C(sp3)−C(sp2)(成键类型),C-N cleavage (其他)

ABSTRACT: Herein, we demonstrate the ability of isonitriles to be used as alkyl radical precursors in a photoredox-catalyzed transformation involving selective C−N cleavage and Csp3−Csp2 bond formation. This protocol allows for the preparation of functionalizedheteroarenes from readily available isonitriles through a decyanation process. Thereaction is general for primary, secondary, and tertiary substrates, includingamino acid derivatives and druglike molecules.

Plan Design

Optimizationof the Reaction Conditions

SelectedSubstrate Scope: Benzylic Isonitriles

SelectedSubstrate Scope: Aliphatic Isonitriles, Amino Acid Derivatives, and BioactiveMolecules

Heteroarylationof Bisisonitriles and Orthogonal Functionalization ofAmino Acids

Prof. Mariola Tortosa etalhave developed the first protocol thatuses isonitriles as alkyl radical precursors in a photoredox-catalyzed transformation involvingselective C−N cleavage and subsequent C−C bond formation. This transformationallows for the interconversion of readily available isonitriles into functionalized pyridines under mild conditions in the presence ofan organic photocatalyst and a silyl amine. Mechanistic studiessuggest a catalytic cycle with reductive quenching involved. Importantly, thereaction can be used to functionalize primary, secondary, and tertiarysubstrates both benzylic and nonbenzylic, thereby expanding significantly thecurrent structural scope. Moreover, we envision that this study will enable thedevelopment of further photocatalyzed transformations using isonitriles to selectively cleave and functionalize C−N bonds.

（转自：康龙化成）

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