1021190-29-3Relevant articles and documents
Distinct Catalytic Performance of Dirhodium(II) Complexes with ortho-Metalated DPPP in Dehydrosilylation of Styrene Derivatives with Alkoxysilanes
Lu, Wenkui,Wu, Xiaoyu,Xie, Xiaomin,Yang, Liqun,Zhang, Zhaoguo,Zhu, Xiaoyu
, p. 10190 - 10197 (2021/08/24)
Herein, we describe dirhodium(II) complexes for the ortho-metalated 1,3-bis(diphenylphosphino)propane (DPPP)-catalyzed dehydrosilylation of vinylarenes with tertiary silanes, particularly alkoxysilanes. This catalytic method displays a broad substrate scope. Both electron-donating and electron-withdrawing substituents on the vinylarenes are well tolerated in this protocol. The dehydrosilylation reactions are compatible with a diverse range of tertiary silanes such as (EtO)3SiH, (TMSO)2MeSiH, (HSiMe2)2O, Et3SiH, and Ph3SiH. Mechanistic studies indicated that a mixture of Rh2(OAc)4, DPPP, and P(OMe)3 provided a stable and rigid dirhodium(II) complex with ortho-metalated DPPP as the bridging ligand and the phosphonate as the axial ligand in the catalytic system. The structure of the dirhodium(II) complexes was also supported by X-ray crystal diffraction. Further experiments confirmed that the dirhodium(II) complexes may be the active species that catalyze the dehydrosilylation reaction. Control experiments showed that norbornene works as the hydrogen acceptor in the reaction and plays a crucial role in the generation of the key catalytic intermediate, a rhodium silicon species.
Xphos ligand and platinum catalysts: A versatile catalyst for the synthesis of functionalized β-(E)-vinylsilanes from terminal alkynes
Hamze, Abdallah,Provot, Olivier,Brion, Jean-Daniel,Alami, Mouad
, p. 2789 - 2797 (2008/12/20)
Hydrosilylation of functionalized terminal arylalkynes with a variety of silanes catalyzed by PtCl2 or PtO2 in the presence of the air-stable and bulky Xphos ligand was investigated. Regardless of the electronic nature (electron withdrawing or donating group) and the position (o, m, p) of the substituents on the aromatic ring, a single β-(E)-styrylsilanes was obtained in good to excellent yields. The regioselectivity of the H-Si bond addition was found to be governed by steric effects induced by the bulky Xphos ligand. A dramatic regioselectivity was also observed when functionalized terminal aliphatic alkynes were employed as a substrate and in these cases regioisomeric β-(E)-vinylsilanes were generated with excellent selectivity.
