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Nickel-Catalyzed Radical Migratory Coupling Enables C-2 Arylation of Carbohydrates.

ABSTRACT: Nickel catalysis offers exciting opportunities to address unmet challenges in organic synthesis. Herein we report the first nickel-catalyzed radical migratory cross-coupling reaction for the direct preparation of 2-aryl-2-deoxyglycosides from readily available 1-bromosugars and arylboronic acids. The reaction features a broad substrate scope and tolerates a wide range of functional groups and complex molecular architectures. Preliminary experimental and computational studies suggest a concerted 1,2-acyloxy rearrangement via a cyclic five-membered-ring transition state followed by nickel-catalyzed carbon-carbon bond formation. The novel reactivity provides an efficient route to valuable C-2-arylated carbohydrate mimics and building blocks, allows for new strategic bond disconnections, and expands the reactivity profile of nickel catalysis.

SUBMITTER: Zhao G

PROVIDER: S-EPMC8418146 | biostudies-literature | 2021 Jun

REPOSITORIES: biostudies-literature

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Nickel-Catalyzed Radical Migratory Coupling Enables C-2 Arylation of Carbohydrates.

Zhao Gaoyuan G Yao Wang W Kevlishvili Ilia I Mauro Jaclyn N JN Liu Peng P Ngai Ming-Yu MY

Journal of the American Chemical Society 20210604 23

Nickel catalysis offers exciting opportunities to address unmet challenges in organic synthesis. Herein we report the first nickel-catalyzed radical migratory cross-coupling reaction for the direct preparation of 2-aryl-2-deoxyglycosides from readily available 1-bromosugars and arylboronic acids. The reaction features a broad substrate scope and tolerates a wide range of functional groups and complex molecular architectures. Preliminary experimental and computational studies suggest a concerted ...[more]

PMID: 34086440

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