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Catalytic enantioselective reductive domino alkyl arylation of acrylates via nickel/photoredox catalysis

ABSTRACT: Nonsteroidal anti-inflammatory drug derivatives (NSAIDs) are an important class of medications. Here we show a visible-light-promoted photoredox/nickel catalyzed approach to construct enantioenriched NSAIDs via a three-component alkyl arylation of acrylates. This reductive cross-electrophile coupling avoids preformed organometallic reagents and replaces stoichiometric metal reductants by an organic reductant (Hantzsch ester). A broad range of functional groups are well-tolerated under mild conditions with high enantioselectivities (up to 93% ee) and good yields (up to 90%). A study of the reaction mechanism, as well as literature precedence, enabled a working reaction mechanism to be presented. Key steps include a reduction of the alkyl bromide to the radical, Giese addition of the alkyl radical to the acrylate and capture of the α-carbonyl radical by the enantioenriched nickel catalyst. Reductive elimination from the proposed Ni(III) intermediate generates the product and forms Ni(I). Enantioenriched α-aryl propionic acids are an important class of nonsteroidal anti-inflammatory medications. Here the authors use a visible-light-promoted photoredox/nickel catalyzed method to form such compunds via a three-component alkyl arylation of acrylates.

SUBMITTER: Qian P

PROVIDER: S-EPMC8595378 | biostudies-literature |

REPOSITORIES: biostudies-literature

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