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- Title
Divergent Reactivity of Stannane and Silane in the Trifluoromethylation of Pd<sup>II</sup>: Cyclic Transition State versus Difluorocarbene Release.
- Authors
Pu, Maoping; Sanhueza, Italo A.; Senol, Erdem; Schoenebeck, Franziska
- Abstract
The transmetalation is a key elementary step in cross‐coupling reactions. Yet, the precise nature of its mechanism and transition state geometry are frequently elusive. This report discloses our study of the transmetalation of [PdII]‐F complexes with the silane‐ and stannane‐based trifluoromethylation agents, R3SiCF3 and R3SnCF3. A divergent reactivity was uncovered, with the stannane showing selective R‐group transfer, and the silane selective CF3‐group transfer. Using a combined experimental and computational approach, we uncovered a hitherto unrecognized transmetalation mechanism with the widely employed R3SiCF3 reagent, explaining its unique activity in metal‐catalyzed trifluoromethylations. While the stannane reacts via a cyclic, 4‐membered transition state, the silane undergoes a fundamentally different pathway and releases a difluorocarbene in the transmetalation event. Molecular dynamics studies clearly reinforced the liberation of a free CF2 carbene, which reacts with [PdII]‐F to ultimately generate [PdII]‐CF3.
- Subjects
STANNANE; METHYLATION; COUPLING reactions (Chemistry); MOLECULAR dynamics; TRANSITION state theory (Chemistry)
- Publication
Angewandte Chemie, 2018, Vol 130, Issue 46, p15301
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.201808229