Catalytic Hydrosilylation of Hydrofluoroolefins (HFOs): Synthesis of New Fluorinated Silanes and Diversity of their Synthetic Character. Issue 33 (10th August 2020)

• Record Type: Journal Article
• Authors: Pavlenko, Natalia V.; Peng, Sheng; Petrov, Viacheslav; Jackson, Andrew; Sun, Xuehui; Sprague, Lee; Yagupolskii, Yurii L.
• Is Part Of: European journal of organic chemistry. Issue 33(2020)
• Page Start: 5425
• Page End: 5435
• Publication Date: 2020-08-10
• Subjects: Homogeneous catalysis -- Defluorination -- Desilylation -- Hydrofluoroolefins -- Hydrosilylation -- Silanes; Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1002/ejoc.202000853
• Languages: English
• ISSNs: 1434-193X

Abstract

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 CF2 =CHCH2 CF3 (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. Abstract : 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.