Catalytic Hydrosilylation of Hydrofluoroolefins (HFOs): Synthesis of New Fluorinated Silanes and Diversity of their Synthetic Character
Natalia V. Pavlenko, Sheng Peng, Viacheslav A. Petrov, Andrew Jackson, Sun Xuehui, L.F. Sprague, Yurii L. Yagupolskii
Abstract
New polyfluorinated silanes were synthesized via the Pt, Rh and Pd catalyzed hydrosilylation of commercially available hydrofluoroolefins (HFOs) in moderate to excellent yields. HFO‐1234yf (2,3,3,3‐tetrafluoropropene‐1) and –1234ze (1,3,3,3‐tetrafluoropropene‐1) were reactive with Pt catalyst to form tetrafluoropropylsilanes along with defluorosilylation products. The Z‐ and E‐isomers of HFO‐1336mzz (1,1,1,4,4,4‐hexafluorobut‐2‐ene) gave the desired silanes with Pd catalysis in good to excellent yields, while with Pt catalyst only the dehydrofluorination product CF 2 =CHCH 2 CF 3 (HFO‐1345czf, 1,1,4,4,4‐pentafluorobut‐1‐ene) was obtained. Synthetic applications of the new polyfluorinated silanes were illustrated by conversion of dichloro(hexafluorobutyl)(methyl)silane to the cyclic trisiloxane, which can serve as a monomer for the preparation of polysiloxanes. In addition, the hexafluorobutylsilanes showed defluorinative reactivity with lithium reagents, thereby demonstrating their synthetic utility as valuable building blocks for further transformations via C–F and C‐Si bond activation.