1400817-72-2Relevant academic research and scientific papers
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.
A Rh(I) complex with an annulated N-heterocyclic carbene ligand for E-selective alkyne hydrosilylation
Tyagi, Akshi,Yadav, Suman,Daw, Prosenjit,Ravi, Chitrakar,Bera, Jitendra K.
, p. 167 - 174 (2019/05/15)
A Rh(I) complex supported by a fused π-conjugated imidazo[1,2-a][1,8]naphthyridine-based N-heterocyclic carbene ligand with a Dipp attachment on the imidazole nitrogen has been synthesized and structurally characterized. The title complex is found to be a
Copper-mediated transformation of organosilanes to nitriles with DMF and ammonium iodide
Wang, Zhen,Chang, Sukbok
supporting information, p. 1990 - 1993 (2013/06/04)
Cyanation of aryl-, diaryldimethyl-, and styrylsilanes was developed for the first time under copper-mediated oxidative conditions using ammonium iodide and DMF as the combined source of nitrogen and carbon atom of the introduced cyano unit, respectively. The reaction was observed to proceed in a two-step process: initial conversion of organosilanes to their iodo intermediates and then cyanation. This method has a broad substrate scope with high functional group tolerance.
Reaction of hydrosilanes with alkynes catalyzed by gold nanoparticles supported on TiO2
Psyllaki, Androniki,Lykakis, Ioannis N.,Stratakis, Manolis
, p. 8724 - 8731 (2012/11/13)
Gold nanoparticles supported on TiO2 (0.8-1.4 mol %) catalyze the β-(E) regioselective hydrosilylation of a variety of functionalized terminal alkynes with alkylhydrosilanes in 1,2-dichloroethane (70 °C). The product yields are excellent, and the reaction times relatively short, while almost equimolar amounts of alkynes and hydrosilanes can be used. Minor side-products in up to 35% relative yield of cis-oxidative (dehydrogenative) disilylation, an unprecedented reaction pathway, are formed in the cases of the less hindered hydrosilanes and alkynes. Triethoxysilane reacts faster and affords apart from β-(E) addition products, minor α-hydrosilylation regio-isomers in upto 15% relative yield. Internal alkynes are generally less reactive or even unreactive. It is proposed that cationic Au(I) species stabilized by the support are the reactive catalytic sites, forming in the presence of hydrosilanes either silyl-Au(III)-H (hydrosilylation pathway) or Au(III)-disilyl species (dehydrogenative disilylation pathway). Regarding the mechanism of hydrosilylation, kinetic experiments are in agreement with silyl carbometallation of the triple bond in the rate determining step of the reaction.
