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Rhodium-catalyzed selective direct arylation of phosphines with aryl bromides.

ABSTRACT: The widespread use of phosphine ligand libraries is frequently hampered by the challenges associated with their modular preparation. Here, we report a protocol that appends arenes to arylphosphines to access a series of biaryl monophosphines via rhodium-catalyzed P(III)-directed ortho C-H activation, enabling unprecedented one-fold, two-fold, and three-fold direct arylation. Our experimental and theoretical findings reveal a mechanism involving oxidative addition of aryl bromides to the Rh catalyst, further ortho C-H metalation via a four-membered cyclometalated ring. Given the ready availability of substrates, our approach opens the door to developing more general methods for the construction of phosphine ligands.

SUBMITTER: Wang D

PROVIDER: S-EPMC9132997 | biostudies-literature | 2022 May

REPOSITORIES: biostudies-literature

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Rhodium-catalyzed selective direct arylation of phosphines with aryl bromides.

Wang Dingyi D Li Mingjie M Shuang Chengdong C Liang Yong Y Zhao Yue Y Wang Minyan M Shi Zhuangzhi Z

Nature communications 20220525 1

The widespread use of phosphine ligand libraries is frequently hampered by the challenges associated with their modular preparation. Here, we report a protocol that appends arenes to arylphosphines to access a series of biaryl monophosphines via rhodium-catalyzed P(III)-directed ortho C-H activation, enabling unprecedented one-fold, two-fold, and three-fold direct arylation. Our experimental and theoretical findings reveal a mechanism involving oxidative addition of aryl bromides to the Rh catal ...[more]

PMID: 35614077

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