Synfacts 2024; 20(01): 0033
DOI: 10.1055/s-0043-1772902
Metals in Synthesis

Rhodium-Catalyzed Addition of Arylsilanes to Electrophiles by π-Coordination-Driven Desilylation

Rezensent(en):
Martin Oestreich
,
Hendrik F. T. Klare
,
Emilio Acuña Bolomey
Lin Y, Shi H. * Westlake University, Hangzhou, P. R. of China
Rhodium-Catalyzed Addition of (Trialkylsilyl)arenes to Electrophiles via π‑Coordination-Driven C–Si Bond Activation.

J. Am. Chem. Soc. 2023;
145: 22753-22761
DOI: 10.1021/jacs.3c08603.
 

Significance

A rhodium(III)-catalyzed desilylation of (trialkylsilyl)arenes with fluoride is reported, giving access to stabilized phenyl anion intermediates that eventually undergo addition to electrophiles. The desilylation is facilitated by the π-coordination of the rhodium complex.


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Comment

Mechanistic as well as computational studies support the shown mechanism, involving nucleophilic addition of the fluoride to the aromatic ring, followed by 1,2-migration and C(sp2)–Si heterolysis.


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Publikationsverlauf

Artikel online veröffentlicht:
08. Dezember 2023

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