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Arylation of Axially Chiral Phosphorothioate Salts by Dinuclear Pd^I Catalysis.

ABSTRACT: S-aryl phosphorothioates are privileged motifs in pharmaceuticals, agrochemicals, and catalysts; yet, the challenge of devising a straightforward synthetic route to enantioenriched S-aryl phosphorothioates has remained unsolved to date. We demonstrate herein the first direct C-SP(=O)(OR')(OR'') coupling of diverse and chiral phosphorothioate salts with aryl iodides, enabled by an air- and moisture-stable Pd^I dimer. Our mechanistic and computational data suggest distinct dinuclear Pd^I catalysis to be operative, which allows for operationally simple couplings with broad scope and full retention of stereochemistry.

SUBMITTER: Chen XY

PROVIDER: S-EPMC6771726 | biostudies-literature | 2019 Aug

REPOSITORIES: biostudies-literature

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Arylation of Axially Chiral Phosphorothioate Salts by Dinuclear PdI Catalysis.

Chen Xiang-Yu XY Pu Maoping M Cheng Hong-Gang HG Sperger Theresa T Schoenebeck Franziska F

Angewandte Chemie (International ed. in English) 20190709 33

S-aryl phosphorothioates are privileged motifs in pharmaceuticals, agrochemicals, and catalysts; yet, the challenge of devising a straightforward synthetic route to enantioenriched S-aryl phosphorothioates has remained unsolved to date. We demonstrate herein the first direct C-SP(=O)(OR')(OR'') coupling of diverse and chiral phosphorothioate salts with aryl iodides, enabled by an air- and moisture-stable PdI dimer. Our mechanistic and computational data suggest distinct dinuclear Pd<s ...[more]

PMID: 31190467

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