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Photoinduced Cobalt-Catalyzed Desymmetrization of Dialdehydes to Access Axial Chirality

Hao Jiang, Xiang‐Kui He, Xuan‐Feng Jiang, Wei Zhao, Liang‐Qiu Lu, Ying Cheng, Wen‐Jing Xiao

2023Journal of the American Chemical Society142 citationsDOI

Abstract

Enantioselective metallaphotoredox catalysis, which combines photoredox catalysis and asymmetric transition-metal catalysis, has become an effective approach to achieve stereoconvergence under mild conditions. Although many impressive synthetic approaches have been developed to access central chirality, the construction of axial chirality by metallaphotoredox catalysis still remains underexplored. Herein, we report two visible light-induced cobalt-catalyzed asymmetric reductive couplings of biaryl dialdehydes to synthesize axially chiral aldehydes (60 examples, up to 98% yield, >19:1 dr, and >99% ee). This protocol shows good functional group tolerance, broad substrate scope, and excellent diastereo- and enantioselectivity.

Topics & Concepts

DesymmetrizationChemistryEnantioselective synthesisChirality (physics)Axial chiralityCatalysisCobaltKinetic resolutionCombinatorial chemistryOrganic chemistrySymmetry breakingChiral symmetry breakingPhysicsNambu–Jona-Lasinio modelQuantum mechanicsAxial and Atropisomeric Chirality SynthesisCatalytic C–H Functionalization MethodsMolecular spectroscopy and chirality
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