327999-89-3Relevant academic research and scientific papers
A Ligand-Free Pt3Cluster Catalyzes the Markovnikov Hydrosilylation of Alkynes with up to 106Turnover Frequencies
Rivero-Crespo, Miguel A.,Leyva-Pérez, Antonio,Corma, Avelino
, p. 1702 - 1708 (2017)
The Pt-catalyzed hydrosilylation of alkynes is the procedure of choice to obtain vinylsilanes, and is claimed to be the most relevant application of Pt in organic synthesis. More than half a century after its discovery, only β-vinylsilanes (anti-Markovnikov addition) are obtained with simple Pt catalysts, whereas α-vinylsilanes (Markovnikov addition) remain elusive compounds. Here the catalysis of the Markovnikov hydrosilylation of terminal alkynes by Pt3clusters, in parts-per-million amounts, to give a wide variety of α-vinylsilanes in reasonable isolated yields and with turnover frequencies that can reach up to one million per hour is reported. Moreover, these α-vinylsilanes are reactive in well-stablished C?C bond-forming cascade reactions, in which the corresponding β-isomers are unreactive. Besides its efficiency and synthetic usefulness, this catalytic system is an excellent example of how the atom-by-atom aggregation of a catalytic metal leads to a different selectivity for a given reaction.
A pronounced ligand effect on platinum-catalyzed Hydrosilylation of terminal alkynes
Dong, Cheng,Yuan, Yang,Cui, Yu-Ming,Zheng, Zhan-Jiang,Cao, Jian,Xu, Zheng,Xu, Li-Wen
, (2018/02/07)
The use of ligands to tune the reactivity and regioselectivity of transition metal-based catalyst for silicon-mediated organic synthesis (SiMOS) is an important topic and challenge in organosilicon chemistry and synthetic organic chemitstry. In this manus
Effect of triarylphosphane ligands on the rhodium-catalyzed hydrosilylation of alkene
Xue, Mei,Li, Jiayun,Peng, Jiajian,Bai, Ying,Zhang, Guodong,Xiao, Wenjun,Lai, Guoqiao
, p. 120 - 126 (2014/02/14)
A series of triarylphosphanes (1a, 2a, 3a, 4a, 5a, 6a, 7a, 8a, 9a, 10a, 11a) have been synthesized. An X-ray crystal structure analysis of (2-bromophenyl)diphenylphosphane (1a) unambiguously confirmed the constitution of the functionalized phosphane. The hydrosilylation reaction of styrene with triethoxysilane catalyzed with RhCl3/triarylphosphane was studied. In comparison with the classic Wilkinson's catalyst, rhodium complexes with functionalized triarylphosphane ligands are characterized by a very high catalytic effectiveness for the hydrosilylation of alkene. Among these catalysts tested, RhCl3/diphenyl(2-(trimethylsilyl)phenyl)phosphane (8a) exhibited excellent catalytic properties. Using this silicon-containing phosphane ligand for the rhodium-catalyzed hydrosilylation of styrene, both higher conversion of alkene and higher β-adduct selectivity were obtained than with Wilkinson's catalyst.
Sequential reactions directed by core/shell catalytic reactors
Wei, Yanhu,Soh, Siowling,Apodaca, Mario M.,Kim, Jiwon,Grzybowski, Bartosz A.
experimental part, p. 857 - 863 (2010/10/03)
Millimeter-sized reactor particles made of permeable polymer doped with catalysts arranged in a core/shell fashion direct sequences of chemical reactions (e.g., alkyne coupling followed by hydrogenation or hydrosilylation followed by hydrogenation). Spati
Olefin ring closing metathesis and hydrosilylation reaction in aqueous medium by grubbs second generation ruthenium catalyst
Polshettiwar, Vivek,Varma, Rajender S.
supporting information; experimental part, p. 7417 - 7419 (2009/05/07)
(Chemical Equation Presented) The Grubbs second generation ruthenium catalyst was shown to catalyze various olefin ring closing metathesis and hydrosilylation reactions in aqueous medium. Reactions proceeded in pure water without any additives or cosolvents, in a short period of time. We found that inhomogeneity of the reaction mixture does not prevent high conversion (70-95%) of the products in both reactions.
