Catalytic Hydrosilylation of Hydrofluoroolefins (HFOs): Synthesis of New Fluorinated Silanes and Diversity of their Synthetic Character

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 for...

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Published in:European journal of organic chemistry 2020-09, Vol.2020 (33), p.5425-5435
Main Authors: Pavlenko, Natalia V., Peng, Sheng, Petrov, Viacheslav, Jackson, Andrew, Sun, Xuehui, Sprague, Lee, Yagupolskii, Yurii L.
Format: Article
Language:English
Subjects:
Catalysis
Catalysts
Chemical synthesis
Defluorination
Desilylation
Homogeneous catalysis
Hydrofluoroolefins
Hydrosilylation
Isomers
Lithium
Palladium
Platinum
Polysiloxanes
Reagents
Silanes
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Summary: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 CF2=CHCH2CF3 (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. We present here the hydrosilylation of commercially available hydrofloroolefins catalyzed by Pt, Pd, and Rh complexes as an efficient route toward a family of new polyfluorinated silanes as well as their use as versatile building blocks for subsequent functionalization based on C–F and C‐Si bond activation.
ISSN:1434-193X
1099-0690
DOI:10.1002/ejoc.202000853