Decarboxylative Phosphine Synthesis: Insights into the Catalytic, Autocatalytic, and Inhibitory Roles of Additives and Intermediates

Phosphines are among the most widely used ligands, catalysts, and reagents. Current synthetic approaches to phosphines are dominated by nucleophilic displacement reactions with organometallic reagents. Here, we report a radical-based approach to phosphines that proceeds by a cross-electrophile coupl...

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Bibliographic Details
Published inACS catalysis Vol. 9; no. 11; pp. 9764 - 9774
Main Authors Jin, Shengfei, Haug, Graham C, Nguyen, Vu T, Flores-Hansen, Carsten, Arman, Hadi D, Larionov, Oleg V
Format Journal Article
LanguageEnglish
Published American Chemical Society 01.11.2019
Subjects
carboxylic acid
biphosphine
phosphine
zinc activation
photocatalysis
autocatalysis
redox-active ester
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Summary:Phosphines are among the most widely used ligands, catalysts, and reagents. Current synthetic approaches to phosphines are dominated by nucleophilic displacement reactions with organometallic reagents. Here, we report a radical-based approach to phosphines that proceeds by a cross-electrophile coupling of chlorophosphines and redox-active esters. The reaction allows for the synthesis of a broad range of substituted phosphines that were not readily attainable with the present methods. Our experimental and DFT computational studies also clarified the catalytic, autocatalytic, and inhibitory roles of additives and intermediates, as well as the mechanistic details of the photocatalytic and zinc-mediated redox modes that can have implications for the mechanistic interpretation of other cross-electrophile coupling reactions.
ISSN:2155-5435
2155-5435
DOI:10.1021/acscatal.9b03366