17988-21-5Relevant articles and documents
Countercation effect on reactivity of o-(fluorodimethylsilyl)phenyl anion
Kawachi, Atsushi,Teranishi, Takuya,Deguchi, Takuma,Yamamoto, Yohsuke
, p. 53 - 57 (2013)
The countercation effect on the reactivity of ambiphilic o-(fluorodimethylsilyl)phenyl anion was investigated by replacing Li in 1 with Cu (4 and 5), Mg (6), and Zn (7). The reactivity of the aryl metal species was estimated by the yields of dimerized pro
Photocatalyzed cross-dehydrogenative coupling of silanes with alcohols and water
Lv, Haiping,Laishram, Ronibala Devi,Chen, Jingchao,Khan, Ruhima,Zhu, Yuanbin,Wu, Shiyuan,Zhang, Jianqiang,Liu, Xingyuan,Fan, Baomin
supporting information, p. 3660 - 3663 (2021/04/16)
An efficient method for the dehydrogenative coupling of silanes with alcohols under photocatalysis was developed. The reaction proceeded in the presence of Ru(bpy)3Cl2(0.5 mol%) under visible light irradiation in acetonitrile at room temperature. The developed methodology was also applicable for the synthesis of silanols using water as a coupling partner.
Phosphirenium ions as masked phosphenium Catalysts: Mechanistic evaluation and application in synthesis
Gasperini, Danila,Neale, Samuel E.,Mahon, Mary F.,MacGregor, Stuart A.,Webster, Ruth L.
, p. 5452 - 5462 (2021/06/01)
The utilization of phosphirenium ions is presented; optimized and broadened three-membered ring construction is described together with the use of these ions as efficient pre-catalysts for metal-free carbonyl reduction with silanes. Full characterization of the phosphirenium ions is presented, and initial experimental and computational mechanistic studies indicate that these act as a "masked phosphenium"source that is accessed via ring opening. Catalysis proceeds via associative transfer of {Ph2P+} to a carbonyl nucleophile, Ha'SiR3 bond addition over the C=O group, and associative displacement of the product by a further equivalent of the carbonyl substrate, which completes the catalytic cycle. A competing off-cycle process leading to vinyl phosphine formation is detailed for the hydrosilylation of benzophenone for which an inverse order in [silane] is observed. Experimentally, the formation of side products, including off-cycle vinyl phosphine, is favored by electrondonating substituents on the phosphirenium cation, while catalytic hydrosilylation is promoted by electron-withdrawing substituents. These observations are rationalized in parallel computational studies.
