2290-47-3Relevant academic research and scientific papers
Synergistic Catalysis by Br?nsted Acid/Carbodicarbene Mimicking Frustrated Lewis Pair-Like Reactivity
Bai, Yuna,Chan, Yi-Chen,Chen, Hsing-Yin,Chen, Hsuan-Ying,Chen, Wen-Ching,Li, Chen-Yu,Ong, Tiow-Gan,Tseng, Mei-Chun,Wu, Ying-Yann,Yap, Glenn P. A.,Zhao, Lili
supporting information, p. 19949 - 19956 (2021/08/03)
Carbodicarbene (CDC), unique carbenic entities bearing two lone pairs of electrons are well-known for their strong Lewis basicity. We demonstrate herein, upon introducing a weak Br?nsted acid benzyl alcohol (BnOH) as a co-modulator, CDC is remolded into a Frustrated Lewis Pair (FLP)-like reactivity. DFT calculation and experimental evidence show BnOH loosely interacting with the binding pocket of CDC via H-bonding and π-π stacking. Four distinct reactions in nature were deployed to demonstrate the viability of proof-of-concept as synergistic FLP/Modulator (CDC/BnOH), demonstrating enhanced catalytic reactivity in cyclotrimerization of isocyanate, polymerization process for L-lactide (LA), methyl methacrylate (MMA) and dehydrosilylation of alcohols. Importantly, the catalytic reactivity of carbodicarbene is uniquely distinct from conventional NHC which relies on only single chemical feature of nucleophilicity. This finding also provides a new spin in diversifying FLP reactivity with co-modulator or co-catalyst.
Use of Silylated Formiates as Hydrosilane Equivalents
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Paragraph 0502-0505, (2021/09/26)
The present invention relates to a method for preparing organic compounds of formula (I) by reaction between a silylated formiate of formula (II) and an organic compound in the presence of a catalyst and optionally of an additive. The invention also relates to use of the method for preparing organic compounds of formula (I) for the preparation of reagents for fine chemistry and for heavy chemistry, as well as in the production of vitamins, pharmaceutical products, adhesives, acrylic fibres, synthetic leathers, and pesticides.
Hydrosilylation of Carbonyls Catalyzed by Hydridoborenium Borate Salts: Lewis Acid Activation and Anion Mediated Pathways
Rawat, Sandeep,Bhandari, Mamta,Porwal, Vishal Kumar,Singh, Sanjay
supporting information, p. 7195 - 7203 (2020/05/18)
The electronically unsaturated three-coordinated hydridoborenium cations [LBH]+[HB(C6F5)3]-(1) and [LBH]+[B(C6F5)4]-(2), supported by a bis(phosphinimino)amide ligand, were found to be excellent catalysts for hydrosilylation of a range of aliphatic and ar
Electrophilic Organobismuth Dication Catalyzes Carbonyl Hydrosilylation
Kannan, Ramkumar,Balasubramaniam, Selvakumar,Kumar, Sandeep,Chambenahalli, Raju,Jemmis, Eluvathingal D.,Venugopal, Ajay
supporting information, p. 12717 - 12721 (2020/09/09)
Bismuth compounds are gaining importance as potential alternatives to transition-metal complexes and electron deficient lighter p-block compounds in homogeneous catalysis. Computational analysis on the two-coordinate [(Me2NC6H4)Bi]2+ possessing three electrophilic sites is experimentally evidenced by the isolation of [{Me2NC6H4}Bi{OP(NMe2)3}3][B(3,5-C6H3Cl2)4]2. These observations led us to generate dicationic organobismuth catalyst, [(Me2NC6H4)Bi(L)3]2+ (L=aldehyde/ketone), evidenced by NMR spectroscopy in solution and by single-crystal X-ray diffraction in the solid state. It efficiently catalyzes hydrosilylation of aldehydes and ketones resulting in silyl ethers as the only products in high yields. Our investigations support a carbonyl activation mechanism at the bismuth center followed by Si?H addition.
Mild synthesis of silyl ethers: Via potassium carbonate catalyzed reactions between alcohols and hydrosilanes
Delucia, Nicholas A.,Das, Nivedita,Vannucci, Aaron K.
, p. 3415 - 3418 (2018/05/23)
A method has been developed for the silanolysis of alcohols using an abundant and non-corrosive base K2CO3 as a catalyst. Reactions between a variety of alcohols and hydrosilanes generate silyl ethers under mild conditions. The use of hydrosilanes leads to the formation of H2 as the only byproduct thus avoiding the formation of stoichiometric strong acids. The mild conditions lead to a wide scope of possible alcohol substrates and good functional group tolerance. Selective alcohol silanolysis is also observed in the presence of reactive C-H bonds, lending this method for extensive use in protection group chemistry.
N-Heterocyclic Olefin Catalyzed Silylation and Hydrosilylation Reactions of Hydroxyl and Carbonyl Compounds
Kaya, U?ur,Tran, Uyen P.N.,Enders, Dieter,Ho, Junming,Nguyen, Thanh V.
supporting information, p. 1398 - 1401 (2017/03/23)
N-Heterocyclic olefins (NHOs), the alkylidene derivatives of N-heterocyclic carbenes (NHCs), have recently emerged as a new family of promising organocatalysts with strong nucleophilicity and Br?nsted basicity. The development of a novel method is shown using NHOs as efficient promoters for the direct dehydrogenative silylation of alcohols or hydrosilylation of carbonyl compounds. Preliminary results of the first NHO-promoted asymmetric synthesis are also discussed.
Controlled hydrosilylation of carbonyls and imines catalyzed by a cationic aluminum alkyl complex
Koller, Juergen,Bergman, Robert G.
scheme or table, p. 2530 - 2533 (2012/06/04)
The synthesis, characterization, and unprecedented catalytic activity of cationic aluminum alkyl complexes toward hydrosilylation are described. X-ray crystallographic analysis of Tp*AlMe2 (1) and [Tp*AlMe][I3] (3) revealed the prefe
Trioxorhena(VII)carborane anion and its methyl-substituted analogue: Synthesis, structure, DFT, and catalytic studies
Pichaandi, Kothanda Rama,Fanwick, Phillip E.,Abu-Omar, Mahdi M.
scheme or table, p. 1888 - 1896 (2012/04/23)
Synthesis and characterization of trioxorhena(VII)carborane [Bu 4N][(η1-C2B9H 11)ReO3] (1a) and its methyl-substituted analogue [Bu 4N][(7,8-Me2-η1-C2
Large-scale preparation and labelling reactions of deuterated silanes
Campos, Jesus,Rubio, Miguel,Esqueda, Ana C.,Carmona, Ernesto
experimental part, p. 29 - 38 (2012/06/30)
A catalytic synthesis of deuterated silanes SiEt3D, SiMe 2PhD and SiPh2D2 is reported that allows their facile generation in a 3-4g scale, utilizing D2 (0.5bar) as the hydrogen isotope source and low
Highly efficient and chemoselective ruthenium-catalyzed hydrosilylation of aldehydes
Do, Youngshil,Han, Junghoon,Rhee, Young Ho,Park, Jaiwook
experimental part, p. 3363 - 3366 (2012/02/01)
The highly chemoselective hydrosilylation of aldehydes was achieved using a ruthenium catalyst activated by a household fluorescent light (30 W) at or below room temperature. The hydrosilylation was almost exclusive to aldehydes over ketones and olefins.
