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Steric Crowding Makes Challenging C(sp3)-F Reductive Eliminations Feasible.


ABSTRACT: A high-yielding fluorination of (triphos)Pt-R(+) has been achieved using an array of F(+) sources, with XeF(2) yielding R-F in minutes. The C-F coupling proved to be a stereoretentive process that proceeds via a concerted reductive elimination from a putative dicationic Pt(IV) center. The larger the steric congestion of the (triphos)Pt-C(sp3) (+) complexes, the more efficient the fluorination, seemingly a result of sterically accelerated C-F reductive elimination along with simultaneous deceleration of its competing processes (?-H elimination).

SUBMITTER: Zhao SB 

PROVIDER: S-EPMC3159157 | biostudies-literature | 2011 Aug

REPOSITORIES: biostudies-literature

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Steric Crowding Makes Challenging C(sp3)-F Reductive Eliminations Feasible.

Zhao Shu-Bin SB   Becker Jennifer J JJ   Gagné Michel R MR  

Organometallics 20110801 15


A high-yielding fluorination of (triphos)Pt-R(+) has been achieved using an array of F(+) sources, with XeF(2) yielding R-F in minutes. The C-F coupling proved to be a stereoretentive process that proceeds via a concerted reductive elimination from a putative dicationic Pt(IV) center. The larger the steric congestion of the (triphos)Pt-C(sp3) (+) complexes, the more efficient the fluorination, seemingly a result of sterically accelerated C-F reductive elimination along with simultaneous decelera  ...[more]

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