39579-23-2Relevant academic research and scientific papers
Primary Alcohols via Nickel Pentacarboxycyclopentadienyl Diamide Catalyzed Hydrosilylation of Terminal Epoxides
Lambert, Tristan H.,Steiniger, Keri A.
supporting information, p. 8013 - 8017 (2021/10/25)
The efficient and regioselective hydrosilylation of epoxides co-catalyzed by a pentacarboxycyclopentadienyl (PCCP) diamide nickel complex and Lewis acid is reported. This method allows for the reductive opening of terminal, monosubstituted epoxides to form unbranched, primary alcohols. A range of substrates including both terminal and nonterminal epoxides are shown to work, and a mechanistic rationale is provided. This work represents the first use of a PCCP derivative as a ligand for transition-metal catalysis.
Dehydrogenative coupling of alcohols and carboxylic acids with hydrosilanes catalyzed by a salen-Mn(v) complex
Vijjamarri, Srikanth,Chidara, Vamshi K.,Rousova, Jana,Du, Guodong
, p. 3886 - 3892 (2016/06/14)
A Mn(v)-salen complex was found to be an effective catalyst for the dehydrogenative coupling of hydroxyl groups with hydrosilane. The reaction conditions were optimized with different silanes and efficient dehydrogenative coupling was achieved by using triethoxysilane and diphenylsilane. Various alcohols and phenols and a limited number of carboxylic acids were converted into the corresponding silyl ethers and silyl esters. A range of functional groups such as chloro, nitro, methoxy, carbonyl and carbon-carbon multiple bonds are tolerated in the reaction.
Iron-Catalyzed Hydrosilylation of Aldehydes and Ketones under Solvent-Free Conditions
Wekesa, Francis S.,Arias-Ugarte, Renzo,Kong, Lydia,Sumner, Zachary,McGovern, Gregory P.,Findlater, Michael
, p. 5051 - 5056 (2015/11/09)
Exposure of aldehyde or ketone to 1 mol % BIAN-Fe(C7H8) complex in the presence of diphenyl silane affords the corresponding protected alcohol in excellent yields, under mild reaction conditions. Aldehydes and ketones are reduced cleanly in the presence of a broad range of functional groups under solvent-free conditions.
POP-pincer silyl complexes of group 9: Rhodium versus iridium
Esteruelas, Miguel A.,Oliván, Montserrat,Vélez, Andrea
, p. 12108 - 12119 (2013/11/19)
9,9-Dimethyl-4,5-bis(diisopropylphosphino)xanthene (xant(P iPr2)2) derivatives RhCl{xant(P iPr2)2} (1) and IrHCl{xant(PiPr 2)[iPrPCH(Me)CH2]} (2) react with diphenylsilane and triethylsilane to give the saturated d6-compounds RhHCl(SiR3){xant(PiPr2)2} (SiR 3 = SiHPh2 (3), SiEt3 (4)) and IrHCl(SiR 3){xant(PiPr2)2} (SiR3 = SiHPh2 (5), SiEt3 (6)). Complexes 3 and 5 undergo a Cl/H position exchange process via the MH{xant(PiPr2) 2} (M = Rh (8), Ir (E)) intermediates. The rhodium complex 3 affords the square planar d8-silyl derivative Rh(SiClPh2) {xant(PiPr2)2} (7), whereas the iridium derivative 5 gives IrH2(SiClPh2){xant(PiPr 2)2} (9), which is stable. In agreement with the formation of 7, the reactions of 8 with silanes are a general method to prepare square planar d8-rhodium-silyl derivatives. Thus, the addition of triethylsilane and triphenylsilane to 8 initially leads to the dihydrides RhH2(SiR3){xant(PiPr2)2} (SiR3 = SiEt3 (10), SiPh3 (11)), which lose molecular hydrogen to afford Rh(SiR3){xant(PiPr 2)2} (SiR3 = SiEt3 (12), SiPh 3 (13)). Treatment of 7 with NaBArF4· 2H2O leads to the cationic five-coordinate d6-species [RhH{Si(OH)Ph2}{xant(PiPr2)2}] BArF4 (14) through a silylene intermediate. According to the participation of the latter in the formation of 14, this cation is an efficient catalyst precursor for the monoalcoholysis of diphenylsilane with a wide range of alcohols, reaching turnover frequencies at 50% of conversion between 4000 and 76 500 h-1. The X-ray structures of 3, 6, 7, 9, 12, and 14 are also reported.
A remarkably active iron catecholate catalyst immobilized in a porous organic Polymer
Kraft, Steven J.,Sanchez, Raul Hernandez,Hock, Adam S.
, p. 826 - 830 (2013/07/25)
A single-site, iron catecholate-containing porous organic polymer was prepared and utilized as a stable and remarkably active catalyst for the hydrosilylation of ketones and aldehydes. In some instances, catalyst loadings of 0.043-2.1 mol % [Fe] were sufficient for complete hydrosilylation of aldehydes and ketones within 15 min at room temperature. The catalyst can be recycled at least three times without a drop in catalytic activity. This system is an example of an immobilized homogeneous catalyst with no homogeneous analogue.
