- Application of an Electrochemical Microflow Reactor for Cyanosilylation: Machine Learning-Assisted Exploration of Suitable Reaction Conditions for Semi-Large-Scale Synthesis
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Cyanosilylation of carbonyl compounds provides protected cyanohydrins, which can be converted into many kinds of compounds such as amino alcohols, amides, esters, and carboxylic acids. In particular, the use of trimethylsilyl cyanide as the sole carbon source can avoid the need for more toxic inorganic cyanides. In this paper, we describe an electrochemically initiated cyanosilylation of carbonyl compounds and its application to a microflow reactor. Furthermore, to identify suitable reaction conditions, which reflect considerations beyond simply a high yield, we demonstrate machine learning-assisted optimization. Machine learning can be used to adjust the current and flow rate at the same time and identify the conditions needed to achieve the best productivity.
- Sato, Eisuke,Fujii, Mayu,Tanaka, Hiroki,Mitsudo, Koichi,Kondo, Masaru,Takizawa, Shinobu,Sasai, Hiroaki,Washio, Takeshi,Ishikawa, Kazunori,Suga, Seiji
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supporting information
p. 16035 - 16044
(2021/09/02)
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- Germyliumylidene: A Versatile Low Valent Group 14 Catalyst
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Bis-NHC stabilized germyliumylidenes [RGe(NHC)2]+ are typically Lewis basic (LB) in nature, owing to their lone pair and coordination of two NHCs to the vacant p-orbitals of the germanium center. However, they can also show Lewis acidity (LA) via Ge?CNHC σ* orbital. Utilizing this unique electronic feature, we report the first example of bis-NHC-stabilized germyliumylidene [MesTerGe(NHC)2]Cl (1), (MesTer=2,6-(2,4,6-Me3C6H2)2C6H3; NHC= IMe4=1,3,4,5-tetramethylimidazol-2-ylidene) catalyzed reduction of CO2 with amines and arylsilane, which proceeds via its Lewis basic nature. In contrast, the Lewis acid nature of 1 is utilized in the catalyzed hydroboration and cyanosilylation of carbonyls, thus highlighting the versatile ambiphilic nature of bis-NHC stabilized germyliumylidenes.
- Sarkar, Debotra,Dutta, Sayan,Weetman, Catherine,Schubert, Emeric,Koley, Debasis,Inoue, Shigeyoshi
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supporting information
p. 13072 - 13078
(2021/08/09)
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- n-Butyllithium as a highly efficient precatalyst for cyanosilylation of aldehydes and ketones
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A highly efficient cyanosilylation protocol mediated by the easily availablen-BuLi with a wide range of aldehydes and ketones was developed. This protocol features excellent yields with very lown-BuLi loadings (0.01-0.05 mol%) at room temperature, solvent
- Kang, Zihan,Wang, Yuhong,Xu, Xiaojuan,Xue, Mingqiang,Zhang, Wenxuan,Zhou, Shuai,Zhu, Xu
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supporting information
p. 7432 - 7437
(2021/09/07)
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- A novel yttrium-based metal-organic framework for the efficient solvent-free catalytic synthesis of cyanohydrin silyl ethers
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A new porous metal-organic framework (MOF) with the chemical formula [Y5L6(OH)3(DMF)3]·5H2O (1) (where L = 3-amino-4-hydroxybenzoate) has been prepared by a solvothermal procedure. The structural char
- Cepeda, Javier,Echenique-Errandonea, Estitxu,Fernández, Ignacio,Pérez, Juana M.,Rodríguez-Diéguez, Antonio,Rojas, Sara,Seco, José M.
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supporting information
p. 11720 - 11724
(2021/09/06)
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- Synthesis of cyanooxovanadate and cyanosilylation of ketones
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The cyanosilylation was performed by using metavanadate catalysts, and in situ measurements revealed the formation of [VO2(CN)3]2- and [VO4TMS2]- under reaction conditions. The reaction of [VO2(CN)3]2-, trimethylsilyl cyanide (TMSCN), and water afforded [
- Hayashi, Yoshihito,Kawabata, Hiroko,Kikukawa, Yuji
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p. 31688 - 31692
(2021/11/30)
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- [Mes-B-TMP]+borinium cation initiated cyanosilylation and catalysed hydrosilylation of ketones and aldehydes
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Two aryl amino borinium cations derived from Cl(Mes)B-NR2(NR2= TMP, HMDS) faced divergent outcomes. As the HMDS-substituted one underwent methyl migration from silicon to boron transforming the putative borinium ion to a silylium ion, [Mes-B-TMP]+can initiate cyanosilylation and catalyse hydrosilylation of ketones and aldehydes.
- Chen, Po-Han,Chiu, Ching-Wen,Hsu, Ching-Pei,Liu, Yi-Hung,Tseng, Hsi-Ching
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supporting information
p. 13732 - 13735
(2021/12/27)
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- Nanoceria as a recyclable catalyst/support for the cyanosilylation of ketones and alcohol oxidation in cascade
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The cyanosilylation of carbonyl compounds is a fundamental reaction in organic synthesis, to give cyanohydrins. Ketones are particularly reluctant to cyanosilane addition and require the action of a catalyst, and despite many soluble Br?nsted and Lewis ac
- Garnes-Portolés, Francisco,Leyva-Pérez, Antonio,Rivero-Crespo, Miguel ángel
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- Ultrathin Near-Infrared Light Activated Nano-Hotplate Catalyst
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A combined photothermal-catalytic system that contains a single active element, without using different entities for separate roles (catalytic vs photothermal), is designed here for efficient catalytic reactions. Herein, ultrathin (sub-6 nm) rectangular-l
- Wu, Xiangyang,Yeow, Edwin K. L.
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- Catalytic Transfer Hydration of Cyanohydrins to α-Hydroxyamides
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We report the palladium(II)-catalyzed transfer hydration of cyanohydrins to α-hydroxyamides by using carboxamides as water donors. This method enables selective hydration of various aldehyde- and ketone-derived cyanohydrins to afford α-mono- and α,α-disubstituted-α-hydroxyamides, respectively, under mild conditions (50 °C, 10 min). The direct conversion of fenofibrate, a drug bearing a benzophenone moiety, into a functionalized α,α-diaryl-α-hydroxyamide was achieved by means of a hydrocyanation-transfer hydration sequence. Preliminary kinetic studies and the synthesis of a site-specifically 18O-labeled α-hydroxyamide demonstrated the carbonyl oxygen transfer from the carboxamide reagent into the α-hydroxyamide product.
- Kanda, Tomoya,Naraoka, Asuka,Naka, Hiroshi
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supporting information
p. 825 - 830
(2019/01/14)
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- Beyond Hydrofunctionalisation: A Well-Defined Calcium Compound Catalysed Mild and Efficient Carbonyl Cyanosilylation
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Organocalcium compounds have been reported as efficient catalysts for various transformations, for cases in which one of the substrates contained an E?H (E=B, N, Si, P) bond. Here, we look at the possibility of employing an organocalcium compound for a tr
- Yadav, Sandeep,Dixit, Ruchi,Vanka, Kumar,Sen, Sakya S.
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supporting information
p. 1269 - 1273
(2018/02/06)
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- Easily accessible lithium compound catalyzed mild and facile hydroboration and cyanosilylation of aldehydes and ketones
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Simple and readily accessible lithium compounds such as 2,6-di-tert-butyl phenolate lithium (1a), 1,1′ dilithioferrocene (1b) and nacnac lithium (1c) are found to be efficient single site catalysts for hydroboration of a range of aldehydes and ketones wit
- Bisai, Milan Kumar,Das, Tamal,Vanka, Kumar,Sen, Sakya S.
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supporting information
p. 6843 - 6846
(2018/06/26)
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- Lewis Acid Rather than Bronsted Acid Sites of Montmorillonite K10 Act as a Powerful and Reusable Green Heterogeneous Catalyst for Rapid Cyanosilylation of Ketones
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A practical green protocol was developed for highly efficient cyanosilylation of various ketones catalyzed by commercial montmorillonite K10, with excellent isolated yields (91-99%). The catalyst can be used as received, and its catalytic strength can be
- Huang, Xiao,Chen, Lin,Ren, Fengying,Yang, Chen,Li, Jianghong,Shi, Kejin,Gou, Xiaojun,Wang, Wei
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p. 439 - 444
(2017/02/24)
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- Chiral rare-earth metal complexes with a tridentate amido-fluorenyl ligand: Syntheses, structures and catalytic performance
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The complexes of rare-earth metals (Y, La, Sm and Lu) with a chiral tridentate amido-fluorenyl ligand were synthesized and characterized. These complexes demonstrated high efficiency in catalyzing both the intramolecular hydroamination of non-activated ol
- Chai, Zhuo,Wang, Yemei,Tang, Mujun,Mu, Xiaolong,Hou, Jinsong,Yang, Gaosheng
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p. 236 - 241
(2017/07/04)
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- Synthesis of magnetically recoverable imidazolium hydrogen carbonate and its application as an N-heterocyclic carbene catalyst to cyanosilylation of aldehydes and ketones
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We prepared a magnetically recoverable imidazolium hydrogen carbonate by immobilizing an imidazolium hydrogen carbonate on magnetite and applied it as an N-heterocyclic carbene catalyst to the cyanosilylation of aldehydes and ketones. By employing the magnetite-supported imidazolium hydrogen carbonate as a catalyst, the cyanosilylation proceeded at 60?°C to provide the corresponding trimethylsilylated cyanohydrin in a fair chemical yield. Moreover, after the reaction, the magnetic catalyst was readily recovered by use of an external magnet and could be reused up to five times.
- Fujii, Akira,Choi, Jun-Chul,Fujita, Ken-ichi
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supporting information
p. 1515 - 1518
(2017/03/24)
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- Synthesis, characterization, and reactivity of lanthanide amides incorporating neutral pyrrole ligand. Isolation and characterization of active catalyst for cyanosilylation of ketones
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A series of lanthanide amido complexes incorporating a neutral pyrrole ligand were synthesized and characterized, and their catalytic activities were studied. Treatment of [(Me3Si)2N]3Ln(μ-Cl)Li(THF)3 with 1 equ
- Wang, Fenhua,Wei, Yun,Wang, Shaowu,Zhu, Xiancui,Zhou, Shuangliu,Yang, Gaosheng,Gu, Xiaoxia,Zhang, Guangchao,Mu, Xiaolong
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- Mechanism-Based inactivation of human cytochrome p450 3A4 by two piperazine-Containing compounds
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Human cytochrome P450 3A4 (CYP3A4) is responsible for the metabolism of more than half of pharmaceutic drugs, and inactivation of CYP3A4 can lead to adverse drug-drug interactions. The substituted imidazole compounds 5-fluoro-2-[4-[(2-phenyl-1H-imidazol-5-yl) methyl]-1-piperazinyl]pyrimidine (SCH 66712) and 1-[(2-ethyl-4-methyl-1H-imidazol-5-yl)methyl]-4-[4-(trifluoromethyl)-2-pyridinyl]piperazine (EMTPP) have been previously identified as mechanism-based inactivators (MBI) of CYP2D6. The present study shows that both SCH 66712 and EMTPP are also MBIs of CYP3A4. Inhibition of CYP3A4 by SCH 66712 and EMTPP was determined to be con-centration, time, and NADPH dependent. In addition, inactivation of CYP3A4 by SCH 66712 was shown to be unaffected by the presence of electrophile scavengers. SCH 66712 displays type I binding to CYP3A4 with a spectral binding constant (Ks) of 42.9 ± 2.9 μM. The partition ratios for SCH 66712 and EMTPP were 11 and 94, respectively. Whole protein mass spectrum analysis revealed 1:1 binding stoichiometry of SCH 66712 and EMTPP to CYP3A4 and a mass increase consistent with adduction by the inactivators without addition of oxygen. Heme adduction was not apparent. Multiple monooxygenation products with each inactivator were observed; no other products were apparent. These are the first MBIs to be shown to be potent inactivators of both CYP2D6 and CYP3A4.
- Bolles, Amanda K.,Fujiwara, Rina,Briggs, Erran D.,Nomeir, Amin A.,Furge, Laura Lowe
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p. 1471 - 1475
(2014/12/11)
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- Efficient synthesis of cyanohydrin trimethylsilyl ethers via 1,2-chemoselective cyanosilylation of carbonyls
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Here we report a sustainable protocol for the cyanosilylation of carbonyl compounds 1a-g and 3a-m using trimethylsilyl cyanide and triphenylphosphine supported on polystyrene as a catalyst under solvent-free conditions. It has been shown that a small amou
- Strappaveccia, Giacomo,Lanari, Daniela,Gelman, Dmitri,Pizzo, Ferdinando,Rosati, Ornelio,Curini, Massimo,Vaccaro, Luigi
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p. 199 - 204
(2013/02/23)
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- Polystyrene-supported TBD as an efficient and reusable organocatalyst for cyanosilylation of aldehydes, ketones, and imines
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Polystyrene-supported TBD (PS-TBD) catalyzes cyanosilylation of both aldehydes and ketones using TMSCN to give the corresponding products in high yields. Imines were also converted into the desired α-cyanoanimes under the same conditions. PS-TBD was easil
- Matsukawa, Satoru,Fujikawa, Syohei
-
supporting information; experimental part
p. 1075 - 1077
(2012/04/17)
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- Imidazolium hydrogen carbonates versus imidazolium carboxylates as organic precatalysts for N-heterocyclic carbene catalyzed reactions
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Imidazolium-2-carboxylates (NHC-CO2 adducts, 3) and (benz)imidazolium hydrogen carbonates ([NHC(H)][HCO3], 4) were independently employed as organic precatalysts for various molecular N-heterocyclic carbene (NHC) catalyzed reactions. NHC-CO2 adducts were obtained by carboxylation in THF of related free NHCs (2), while the synthesis of [NHC(H)][HCO3] precursors was directly achieved by anion metathesis of imidazolium halides (1) using potassium hydrogen carbonate (KHCO3) in methanolic solution, without the need for the prior preparation of free carbenes. Thermogravimetric analysis (TGA) and TGA coupled with mass spectrometry (TGA-MS) of most [NHC(H)][HCO3] precursors 4 showed a degradation profile in stages, with either a concomitant or a stepwise release of H2O and CO2, between 108 and 280 °C, depending on the nature of the azolium and substituents. In solution, NHC generation from both [NHC(H)][HCO3] salts and NHC-CO2 adducts could be achieved at room temperature, most likely by a simple solvation effect. Both types of precursors proved efficient for organocatalyzed molecular reactions, including cyanosilylation, benzoin condensation, and transesterification reactions. The catalytic efficiencies of NHC-CO2 adducts 3 were found to be approximately 3 times higher than those of their [NHC(H)][HCO3] counterparts 4.
- Fevre, Mareva,Coupillaud, Paul,Miqueu, Karinne,Sotiropoulos, Jean-Marc,Vignolle, Joan,Taton, Daniel
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p. 10135 - 10144
(2013/01/15)
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- Mild and efficient trimethylsilylcyanation of ketones catalysed by PNP chloride
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Mild & green: The commercially and readily available PNPCl behaves as a very effective catalyst for the synthesis of various trimethylsilyl cyanohydrins from a wide range of aliphatic, cyclic, α,β-unsaturated and aromatic ketones. The method proceeds at r
- Lacour, Marie-Agnes,Rahier, Nicolas J.,Taillefer, Marc
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supporting information; experimental part
p. 12276 - 12279
(2011/12/15)
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- Polymer-supported, carbon dioxide-protected n-heterocyclic carbenes: Synthesis and application in organo- and organometallic catalysis
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The synthesis of a resin-supported, carbon dioxide-protected N-heterocyclic carbene (NHC) and its use in organocatalysis and organometallic catalysis are described. The resin-bound carbon dioxide-protected NHC-based catalyst was prepared via ring-opening
- Pawar, Gajanan Manohar,Buchmeiser, Michael R.
-
scheme or table
p. 917 - 928
(2010/06/15)
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- Organocatalytic synthesis of cyanohydrin trimethylsilyl ethers by potassium 4-benzylpiperidinedithiocarbamate under solvent-free conditions
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Potassium 4-benzylpiperidinedithiocarbamate was found to be an efficient organocatalyst for facile addition of trimethylsilyl cyanide to a wide variety of aldehydes and ketones to afford corresponding cyanohydrin trimethylsilyl ethers in high to quantitat
- Dekamin, Mohammad G.,Alizadeh, Roghieh,Naimi-Jamal, M. Reza
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experimental part
p. 229 - 235
(2010/11/17)
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- Alkali salt of L-proline as an efficient and practical catalyst for the cyanosilylation of a wide variety of carbonyl compounds under solvent-free conditions
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The alkali salt of L-proline was demonstrated to be an efficient and practical catalyst for the cyanosilylation of a wide variety of simple and functionalized carbonyl compounds under solvent-free conditions. The reactions proceeded smoothly at room temperature to afford the corresponding cyanohydrins in good to excellent yields. Copyright Taylor & Francis Group, LLC.
- Shen, Zhi-Liang,Ji, Shun-Jun
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experimental part
p. 775 - 791
(2009/08/08)
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- A dream combination for catalysis: Highly reactive and recyclable scandium(iii) triflate-catalyzed cyanosilylations of carbonyl compounds in an ionic liquid
-
The catalytic activity of lanthanide triflates, particularly scandium triflate, increased dramatically in [bmim][SbF6], allowing the cyanosilylation of a variety of aldehydes and ketones with a turnover frequency up to 48000 mol h-1 and a total turnover number of 100000.
- Park, Boyoung Y.,Ryu, Ka Yeon,Park, Jung Hwan,Lee, Sang-Gi
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experimental part
p. 946 - 948
(2010/04/23)
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- Highly efficient cyanosilylation of sterically bulky ketones catalyzed by tin ion-exchanged montmorillonite
-
Tin ion-exchanged montmorillonite (SnMont) was found to be a powerful catalyst for the cyanosilylation of aromatic and aliphatic ketones having a carbonyl group in sterically congested circumstances with cyanotrimethylsilane, giving the corresponding cyan
- Wang, Jiacheng,Masui, Yoichi,Watanabe, Kenya,Onaka, Makoto
-
supporting information; experimental part
p. 553 - 557
(2009/10/25)
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- Tris(2,4,6-trimethoxyphenyl)phosphine (TTMPP): Efficient catalysts for the cyanosilylation and cyanocarbonation of aldehydes and ketones
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A variety of aldehydes and ketones were transformed to their corresponding cyanohydrin silyl ethers in good to excellent yields in the presence of 1-5 mol% of tris(2,4,6-trimethoxyphenyl)phosphine (TTMPP). Cyanohydrin carbonates were also readily prepared using 5-10 mol% of TTMPP as an organocatalyst.
- Matsukawa, Satoru,Sekine, Izumi,Iitsuka, Ayumi
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experimental part
p. 3353 - 3359
(2009/12/26)
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- Highly efficient synthesis of functionalized tertiary alcohols catalyzed by potassium alkoxide-crown ether complexes
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A highly efficient Mukaiyama aldol reaction between ketones and trimethylsilyl enolates in the presence of potassium alkoxide-crown ether complexes as Lewis base catalysts (0.3-5 mol %), which minimized the competing retro-aldol reaction, was developed. T
- Hatano, Manabu,Suzuki, Shinji,Takagi, Eri,Ishihara, Kazuaki
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supporting information; experimental part
p. 3171 - 3174
(2009/08/09)
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- An expeditious synthesis of cyanohydrin trimethylsilyl ethers using tetraethylammonium 2-(carbamoyl)benzoate as a bifunctional organocatalyst
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Phthalimide and tetraethylammonium hydroxide react via an unusual pathway to afford tetraethylammonium 2-(carbamoyl)benzoate (TEACB) which is of interest as a bifunctional organocatalyst. TEACB (0.5 mol %) was found to catalyze the addition of trimethylsi
- Dekamin, Mohammad G.,Sagheb-Asl, Solmaz,Reza Naimi-Jamal
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scheme or table
p. 4063 - 4066
(2009/10/11)
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- Cyanosilylation of aldehydes and ketones catalyzed by nanocrystalline magnesium oxide
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Cyanosilylation of various aldehydes and ketones with TMSCN proceeded smoothly under mild conditions to give the corresponding cyanohydrin trimethylsilyl ethers in the presence of nanocrystalline magnesium oxide. The cyanohydrin trimethylsilyl ethers of aldehydes produced cyanohydrins in good to high yields on treatment with 2 N HCl. 29Si NMR spectral evidence proved that the reaction proceeds through the hypervalent silicate species by coordination to O2-/O- (Lewis basic site) of nanocrystalline magnesium oxide. Copyright Taylor & Francis Group, LLC.
- Lakshmi Kantam,Mahendar, Koosam,Sreedhar, Bojja,Vijay Kumar,Choudary
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experimental part
p. 3919 - 3936
(2009/04/11)
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- Gold(III)-catalyzed cyanosilylation of ketones and aldehydes
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Gold(III) chloride was found to be a highly efficient catalyst for the cyanosilylation of various ketones and aldehydes. The reactions were complete within 30 minutes at room temperature in the presence of only one mol% gold(III) chloride, yielding the co
- Woo, Kyung Cho,Sung, Min Kang,Medda, Amiya K.,Lee, Jungkyu K.,Choi, Insung S.,Lee, Hee-Seung
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p. 507 - 510
(2008/12/21)
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- Catalytic cyanosilylation of ketones with simple phosphonium salt
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In the presence of 1-5 mol % of benzyltriphenylphosphonium chloride, a wide variety of unconjugated and conjugated, acyclic and cyclic ketones were transformed to their corresponding cyanohydrin silyl ethers in excellent yields.
- Wang, Xiu,Tian, Shi-Kai
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p. 6010 - 6013
(2008/02/10)
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- Fe(Cp)2PF6: An efficient catalyst for cyanosilylation of carbonyl compounds under solvent free condition
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An efficient method for the addition of trimethylsilyl cyanide (TMSCN) to various aldehydes and ketones has been described using Fe(Cp)2PF6 (2.5 mol%) as a catalyst under solvent free condition. Excellent yields of trimethylsilylethe
- Khan, Noor-ul H.,Agrawal, Santosh,Kureshy, Rukhsana I.,Abdi, Sayed H.R.,Singh, Surendra,Jasra, Raksh V.
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p. 4361 - 4366
(2008/02/13)
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- Activation of TMSCN by N-heterocyclic carbenes for facile cyanosilylation of carbonyl compounds
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N-Heterocyclic carbenes were found to be highly effective organocatalysts in activating TMSCN for facile cyanosilylation of carbonyl compounds. Cyano transfer from TMSCN to aldehydes and ketones proceeds at room temperature in the presence of only 0.01-0.
- Song, Jinhua J.,Gallou, Fabrice,Reeves, Jonathan T.,Tan, Zhulin,Yee, Nathan K.,Senanayake, Chris H.
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p. 1273 - 1276
(2007/10/03)
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- Dodecatungestophosphoric acid (H3PW12O40) as a solid green Br?nsted acid catalyzes high yielding and efficient trimethylcyanosylilation reactions of aldehydes and ketones by trimethylsilyl cyanide
-
An efficient solvent-free method is described for the addition of TMSCN to carbonyl groups employing dodecatungestophosphoric acid (H3PW 12O40) as a heterogeneous and environmentally benign catalyst. By this method, aromat
- Firouzabadi, Habib,Iranpoor, Nasser,Jafari, Abbas Ali
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p. 1556 - 1559
(2007/10/03)
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- P(RNCH2CH2)N: Efficient catalysts for the cyanosilylation of aldehydes and ketones
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The 1,2-addition of trialkylsilylcyanides to aldehydes and ketones produces the corresponding protected cyanohydrins in good to excellent yields when carried out at 0°C to room temperature in the presence of catalytic amounts of the nonionic strong base P(RNCH2CH2)N (R = Me, i-Pr) in THF. These catalysts are easily removed from the product by hydrolysis or column filtration through silica gel.
- Fetterly, Brandon M.,Verkade, John G.
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p. 8061 - 8066
(2007/10/03)
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- Iodine as novel reagent for the 1,2-addition of trimethylsilyl cyanide to ketones including α,β-unsaturated ketones
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Molecular iodine is found to catalyze efficiently the addition of trimethylsilyl cyanide to a range of simple and functionalized ketones under very mild and convenient conditions to afford the corresponding cyanohydrin trimethylsilyl ethers in excellent y
- Yadav,Reddy,Reddy, M. Sridhar,Prasad
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p. 9703 - 9706
(2007/10/03)
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- P(MeNMCH2CH2)3N: An effective catalyst for trimethylsilycyanation of aldehydes and ketones
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The title non-ionic phosphazane base promotes the trimethylsilycyanation of alkyl and alkyl aldehydes and ketones in moderate to high yields at room temperature. 29Si-NMR spectral evidence for the intermediacy of a phosphazane phosphorus-silicon adduct is presented.
- Wang, Zhigang,Fetterly, Brandon,Verkade, John G
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p. 161 - 166
(2007/10/03)
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- Regioselective superacid-catalyzed electrocyclization of diphenylmethyl cations to fluorenes, phenanthrols and benzofurans
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Cationic electrocyclization of α-benzoyldiphenylmethanols in the presence of superacid provides fluorenes, phenanthrols and benzofurans in good to moderate yields. A single substitution leads to regioselective cationic electrocyclizations.
- Yoshida,Ohwada
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p. 1487 - 1494
(2007/10/03)
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- A direct and efficient synthetic method for nitriles from ketones
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Cyclic cyano derivatives 3 were obtained by the reaction of Me3SiCN / ZnI2 with the cyclic ketones 2 which gave the trimethylsilyloxy nitriles 4. They were directly transformed to cyano derivatives 3 (70-80% yield) by the reductive reagent Me3SiCl-NaI in acetonitrile in the presence of H2O.
- Kloubert, Stephane,Mathe-Allainmat, Monique,Andrieux, Jean,Langlois, Michel
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p. 2873 - 2887
(2007/10/03)
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- Addition of trimethylsilyl cyanide to aromatic ketones promoted by organic solutions of lithium salts
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Cyanosilylation of aromatic ketones is strongly promoted in organic solutions of specific lithium salts (perchlorate and tetrafluoroborate). Acetonitrile solutions of LiBF4 are safe and efficient media for this reaction.
- Jenner, Gerard
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p. 491 - 494
(2007/10/03)
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- Trimethylsilyl bis(fluorosulfonyl)imide: An efficient catalyst for the addition of trimethylsilyl cyanide to carbonyl compounds
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In the presence of 1 mol% of trimethylsilyl bis(fluorosulfonyl)imide, trimethylsilyl cyanide adds efficiently to carbonyl compounds. The catalyst has been found to be more active than trimethylsilyl triflate for the above reaction.
- Kaur, Harpinder,Kaur, Gurmeet,Trehan, Sanjay
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p. 1925 - 1929
(2007/10/03)
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- Calcined MgAlCO3-HT catalysed cyanosilylation of carbonyl compounds and nucleophilic ring opening of oxiranes using TMSCN
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Nucleophilic addition of TMSCN to carbonyl compounds is found to be catalysed efficiently using hydrotalcite as a solid base. The catalyst is also found to be active in the nucleophilic ring opening of oxiranes giving high regioselectivity.
- Choudary,Narender,Bhuma
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p. 2829 - 2836
(2007/10/02)
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- Reduction of α-Trialkylsiloxy Nitriles with Diisobutylaluminium Hydride (DIBAH): A Facile Preparation of α-Trialkylsiloxy Aldehydes and their Derivatives
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The stepwise synthesis of α-trimethylsiloxy aldehydes and α-hydroxy aldehydes could be achieved via the reduction of α-trimethylsiloxy nitriles with diisobutylaluminium hydride (DIBAH) starting from a variety of ketones.The facile synthesis of optically active α-tert-butyldimethylsiloxy aldehydes was attained by combination of asymmetric silylcyanation of aldehydes and DIBAH reduction of optically active α-siloxy nitriles.Furthermore, in the reduction of some α-tert-butyldimethylsiloxy-β,γ-unsaturated nitriles, migration of the double bond took place to form more stable α-siloxy-α,β-unsaturated aldehydes under some reaction conditions.
- Hayashi, Masahiko,Yoshiga, Tomoko,Nakatani, Kanako,Ono, Kazuyuki,Oguni, Nobuki
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p. 2821 - 2830
(2007/10/02)
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- Solid Acid and Base-Catalyzed Cyanosilylation of Carbonyl Compounds with Cyanotrimethylsilane
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A new attempt was investigated to utilize inorganic solid acids and bases for the promotion of the reaction of cyanotrimethylsilane (Me3SiCN) with carbonyl compounds.Strongly acidic solids, such as Sn4+ ion-exchanged montmorillonite (Sn-Mont) and Fe3+ ion-exchanged montmorillonite (Fe-Mont), as well as basic solids, such as calcium fluoride (CaF2), hydroxyapatite (HAp), calcium oxide (CaO), and magnesium oxide (MgO), catalyzed the reaction of Me3SiCN with aldehydes and ketones to afford the corresponding 2-(trimethylsiloxy)alkanenitriles in good yields.The reactions of dimethyl acetals with Me3SiCN in the presence of solid acids afforded 2-methoxyalkanenitriles.In cyanosilylation of α,β-unsaturated ketones two kinds of adducts were produced selectively, depending on the use of a solid acid or a solid base: 1,4-Adducts (trimethylsilyl enol ether forms) were selectively obtained in the presence of strong solid acids, such as Fe-Mont and Sn-Mont, while 1,2-adducts (trimethylsilyl ether forms) were predominantly formed in the presence of solid bases, such as HAp, CaO, and MgO.The solid acids and bases realized higher activities and selectivities in the cyanosilylation than did conventional homogeneous catalysts.
- Higuchi, Katsumi,Onaka, Makoto,Izumi, Yusuke
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p. 2016 - 2032
(2007/10/02)
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- Efficient Solid Catalyst Systems for Cyanosilylation of Carbonyl Compounds with Cyanotrimethylsilane
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Clay montmorillonite, calcium fluoride, and hydroxyapatite are found to be effective solid catalysts for the reactions of cyanotrimethylsilane with carbonyl compounds.Different catalytic functions of the solid catalysts are also elucidated.
- Onaka, Makoto,Higuchi, Katsumi,Sugita, Keisuke,Izumi, Yusuke
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p. 1393 - 1396
(2007/10/02)
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- A Convenient One-Pot Cyanosilylation of Aldehydes and Ketones Using Potassium or Sodium Cyanide Impregnated on Amberlite XAD Resin and Trimethylsilyl Chloride
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In the cyanosylilation of benzaldehyde, the combination of potassium or sodium cyanide impregnated on Amberlite XAD resin and trimethylsilyl chloride has been found to be a good one-pot cyanosilylation agent.Although acetonitrile is the best solvent, subs
- Sukata, Kazuaki
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p. 3820 - 3822
(2007/10/02)
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- SYNTHESIS OF α-HYDROXIAMIDES VIA THE CYANOSILYLATION OF AROMATIC KETONES
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The trimethylsilyl ethers of the cyanohydrins of aryl-alkyl ketones and diaryl ketones afforded the corresponding α-hydroxyamides upon hydrolysis with HCl or HNO3/HCO2H.The method is advantageous for ketones do not readily undergo addition of HCN.
- Grunewald, Gary L.,Brouillette, Wayne J.,Finney, Jay A.
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p. 1219 - 1220
(2007/10/02)
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