22034-19-1Relevant academic research and scientific papers
Tuning the Selectivity of AuPd Nanoalloys towards Selective Dehydrogenative Alkyne Silylation
Wissing, Maren,Studer, Armido
, p. 5870 - 5874 (2019)
The cross-dehydrogenative coupling of terminal alkynes and hydrosilanes catalyzed by AuPd nanoalloys is described. Metal nanoparticles are readily prepared in 15 minutes from commercially available and cheap starting materials by using a photochemical app
Origin and Control of Chemoselectivity in Cytochrome c Catalyzed Carbene Transfer into Si-H and N-H bonds
Garcia-Borràs, Marc,Kan, S. B. Jennifer,Lewis, Russell D.,Tang, Allison,Jimenez-Osés, Gonzalo,Arnold, Frances H.,Houk
, p. 7114 - 7123 (2021)
A cytochrome c heme protein was recently engineered to catalyze the formation of carbon-silicon bonds via carbene insertion into Si-H bonds, a reaction that was not previously known to be catalyzed by a protein. High chemoselectivity toward C-Si bond formation over competing C-N bond formation was achieved, although this trait was not screened for during directed evolution. Using computational and experimental tools, we now establish that activity and chemoselectivity are modulated by conformational dynamics of a protein loop that covers the substrate access to the iron-carbene active species. Mutagenesis of residues computationally predicted to control the loop conformation altered the protein's chemoselectivity from preferred silylation to preferred amination of a substrate containing both N-H and Si-H functionalities. We demonstrate that information on protein structure and conformational dynamics, combined with knowledge of mechanism, leads to understanding of how non-natural and selective chemical transformations can be introduced into the biological world.
Silyl-pyridine-amine pincer-ligated iridium complexes for catalytic silane deuteration: Via room temperature C-D bond activation of benzene- d 6
Komuro, Takashi,Osawa, Tomohiro,Suzuki, Ryuju,Mochizuki, Daiki,Higashi, Hironori,Tobita, Hiromi
, p. 957 - 960 (2019)
Iridium-hydrido complexes bearing a hemilabile silyl-pyridine-amine pincer ligand were synthesised. They were found to catalyse Si-H deuteration of trialkylsilanes with excess benzene-d6 in 99-94% conversion at room temperature through C-D bond
Regioselective Hydroalkylation of Vinylarenes by Cooperative Cu and Ni Catalysis
Ravn, Anne K.,Johansen, Martin B.,Skrydstrup, Troels
supporting information, (2021/12/14)
Disclosed here is a dual copper and nickel catalytic system with a silyl hydride source for promoting the linear selective hydroalkylation of vinylarenes. This carbon–carbon bond-forming protocol is applied to couple a variety of functionalized vinylarenes with alkyl halides applying a nickel(II) NNN pincer complex in the presence of an NHC-ligated copper catalyst. This combination allows for a 1 mol % loading of the nickel catalyst leading to turnover numbers of up to 72. Over 40 examples are presented, including applications for pharmaceutical diversification. Labeling experiments demonstrated the regioselectivity of the reaction and revealed that the copper catalyst plays a crucial role in enhancing the rate for formation of the reactive linear alkyl nickel complex. Overall, the presented work provides a complimentary approach for hydroalkylation reactions, whilst providing a preliminary mechanistic understanding of the cooperativity between the copper and nickel complexes.
A General Rhodium Catalyst for the Deuteration of Boranes and Hydrides of the Group 14 Elements
Esteruelas, Miguel A.,Martínez, Antonio,Oliván, Montserrat,Vélez, Andrea
, p. 15693 - 15698 (2020/12/02)
Pinacolborane, catecholborane, triethylsilane, triphenylsilane, dimethylphenylsilane, 1,1,1,3,5,5,5-heptamethyltrisiloxane, triethylgermane, triphenylgermane, and triphenylstannane deuterated at the heteroatom position have been catalytically prepared in
Visible-light-mediated deuteration of silanes with deuterium oxide
Zhou, Rong,Li, Jiesheng,Cheo, Han Wen,Chua, Rachel,Zhan, Gu,Hou, Zhaomin,Wu, Jie
, p. 7340 - 7344 (2019/08/20)
Isotopically labeled compounds are highly desirable as they can serve as both mechanistic probes in chemistry and diagnostic tools in medicinal research. Herein, we report an unprecedented visible-light-mediated metal-free deuteration of silanes using Ds
Air- and water-stable Lewis acids: Synthesis and reactivity of P-trifluoromethyl electrophilic phosphonium cations
Fasano,LaFortune,Bayne,Ingleson,Stephan
supporting information, p. 662 - 665 (2018/02/06)
A new class of electrophilic phosphonium cations (EPCs) containing a -CF3 group attached to the phosphorus(v) center is readily accessible in high yields, via a scalable process. These species are stable to air, water, alcohol and strong Br?nsted acid, even at raised temperatures. Thus, P-CF3 EPCs are more robust than previously reported EPCs containing P-X moieties (X = F, Cl, OR), and despite their reduced Lewis acidity they function as Lewis acid catalysts without requiring anhydrous reaction conditions.
Silicone wastes as reducing agents for carbon dioxide transformation: Fluoride-catalyzed formic acid synthesis from CO2, H2O, and disilanes
Motokura, Ken,Naijo, Masaki,Yamaguchi, Sho,Miyaji, Akimitsu,Baba, Toshihide
supporting information, p. 1464 - 1466 (2015/11/24)
Disilanes were found to be reactive reducing agents for the transformation of carbon dioxide to formic acid in the presence of H2O. The reaction is catalyzed by fluoride salts such as tetrabutylammonium fluoride. Isotopic experiments revealed that the proposed reaction pathway includes Si-Si bond cleavage to afford hydrosilane followed by the hydrosilylation of CO2, and, finally, the hydrolysis of silyl formate.
Selective Silylative Reduction of Pyridines Leading to Structurally Diverse Azacyclic Compounds with the Formation of sp3 C-Si Bonds
Gandhamsetty, Narasimhulu,Park, Sehoon,Chang, Sukbok
supporting information, p. 15176 - 15184 (2015/12/18)
Tris(pentafluorophenyl)borane-catalyzed silylative reduction of pyridines has been developed giving rise to the formation of sp3 C-Si bonds selectively beta to the nitrogen atom of azacyclic products. Depending on the position and nature of pyridine substituents, structurally diverse azacycles are obtained with high selectivity under the borane catalysis. Mechanistic studies elucidated the sequence of hydrosilylation in this multiple reduction cascade: 1,2- or 1,4-hydrosilylation as an initial step depending on the substituent position, followed by selective hydrosilylation of enamine double bonds eventually affording β-silylated azacyclic compounds.
Reduction of quinolines to 1,2,3,4-tetrahydroquinolines with hydrosilane/ethanol catalyzed by TiO2-supported gold nanoparticles under solvent free conditions
Louka, Anastasia,Gryparis, Charis,Stratakis, Manolis
, p. 38 - 51 (2015/04/22)
Gold nanoparticles supported on TiO2 (1 mol%) catalyze the reduction of a series of functionalized quinolines into 1,2,3,4-tetrahydroquinolines using hydrosilanes/ethanol (hydride/proton) as the reductant system. A typical reaction requires 4 molar equivalents of phenyldimethylsilane (reductant of choice), 4 molar equivalents of ethanol as a reagent and heating to 70 °C under solvent free conditions. The isolated yields are moderate to excellent and in certain cases the reaction rate is exceedingly fast. Mechanistic analysis revealed the stereoselective addition of two hydrides (from hydrosilane) on positions C2 and C4 of the quinoline ring and two protons (from ethanol) on positions C3 and the nitrogen atom.
