- Cyanosilylation of ketones catalyzed by quaternary ammonium salt and N-oxide
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Dibenzyldimethyl ammonium bromide and triethanolamine N-oxide catalyze the formation of cyanohydrin trimethylsilyl ethers of ketones in 80-99% yield.
- Zhou, Hui,Chen, Fu-Xue,Qin, Bo,Feng, Xiaoming,Zhang, Guolin
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- Construction of tetrasubstituted carbon by an organocatalyst: Cyanation reaction of ketones and ketimines catalyzed by a nucleophilic N-heterocyclic carbene
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A method for cyanation reaction of ketones and ketimines having lower reactivity than aldehydes and aldimines with TMSCN in the presence of N-heterocyclic carbene prepared from 1,3-bis(2,4,6-trimethylphenyl)imidazolium chloride and potassium tert-butoxide
- Fukuda, Yoshimasa,Kondo, Kazuhiro,Aoyama, Toyohiko
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- Efficient and Regioselective Cyanosilylation of Cyclohex-2-enone and Other Unsaturated Ketones over Solid Acid and Base Catalyst
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Cyanotrimethylsilane reacts with α,β-unsaturated ketones to afford 1,4- and 1,2-adducts regioselectively in the presence of strongly acidic montmorillonite and strongly basic CaO or MgO, respectively.
- Higuchi, Katsumi,Onaka, Makoto,Izumi, Yusuke
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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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- Catalytic cyanosilylation of ketones using organic catalyst 1,1,3,3-tetramethylguanidine
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1,1,3,3-Tetramethylguanidine acts as a highly effective catalyst for cyanosilylation of various ketones and aldehydes to the corresponding cyanohydrin trimethylsilyl ethers in up to 99% yield. The reaction proceeds smoothly with 0.1 mol % catalyst loading
- Wang, Lijia,Huang, Xiao,Jiang, Jun,Liu, Xiaohua,Feng, Xiaoming
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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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- Phenolic N-oxide as a highly efficient organocatalyst for cyanosilylation of ketones
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The use of an inexpensive, easy to handle and readily available chemical, 5 mol% phenolic N-oxide, alone as a catalyst for cyanosilylation of ketones gave the corresponding products in 78-99% yield with reaction times of 0.5-16 hours.
- Li, Yan,He, Bin,Feng, Xiaoming,Zhang, Guolin
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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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- 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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- A convenient catalytic procedure for the addition of trimethylsilyl cyanide to functionalised ketones, mediated by InBr3 - Insight into the reaction mechanism
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This paper describes a useful and practical methodology for the addition of trimethylsilyl cyanide (TMSCN) to a large variety of functionalised and unfunctionalised ketones in the presence of catalytic amounts of anhydrous InBr3. The optimum pr
- Bandini, Marco,Cozzi, Pier Giorgio,Garelli, Andrea,Melchiorre, Paolo,Umani-Ronchi, Achille
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- Mild and efficient silylcyanation of ketones catalyzed by cesium fluoride
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An efficient method of addition of trimethylsilylcyanide to ketones by employing cesium fluoride as catalyst has been described. A variety of aromatic, aliphatic, cyclic and heterocyclic ketones have been converted into their corresponding trimethylsilyl
- Kim, Sung Soo,Rajagopal, Gurusamy,Song, Dae Ho
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- Mild and Efficient Silylcyanation of Ketones Catalyzed by N-Methylmorpholine N- Oxide
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An efficient method for achiral addition of TMSCN to ketones by employing N-methylmorpholine N-oxide (NMO) alone as the catalyst is described. A variety of aromatic, aliphatic, cyclic and heterocyclic ketones are converted into their corresponding trimeth
- Kim, Sung Soo,Kim, Dong Won,Rajagopal, Gurusamy
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- Achiral phenolic N-oxides as additives: An alternative strategy for asymmetric cyanosilylation of ketones
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The activation of chiral titanium(IV) complexes with additives, phenolic N-oxides, is found to provide an alternative strategy for asymmetric cyanosilylation of ketones in excellent yield with up to 82% ee.
- He, Bin,Chen, Fu-Xue,Li, Yan,Feng, Xiaoming,Zhang, Guolin
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- Rasta resin-PPh3BnCl and its use in chromatography-free carbonyl cyanosilylation reactions
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Rasta resin-PPhnCl, a new heterogeneous polystyrene-based phosphonium salt, has been synthesized and used to catalyze cyanosilylation reactions of aldehydes and ketones. It was found to be more efficient as a catalyst than a similar heterogeneous phosphon
- Teng, Yan,Toy, Patrick H.
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supporting information; experimental part
p. 551 - 554
(2011/04/23)
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- Robust and efficient, yet uncatalyzed, synthesis of trialkylsilyl-protected cyanohydrins from ketones
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(Chemical Equation Presented) High-yielding cyanosilylation of ketones with NaCN and various chlorotrialkylsilanes in DMSO proceeds smoothly without catalysis to give silyl-protected ketone cyanohydrins. The unique role of DMSO consists in rendering naked
- Cabirol, Fabien L.,Lim, Angela E. C.,Hanefeld, Ulf,Sheldon, Roger A.,Lyapkalo, Ilya M.
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p. 2446 - 2449
(2008/09/19)
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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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- Neutral π-nucleophile-catalyzed cyanation of aldehydes and ketones
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1-Methoxy-2-methyl-1-(trimethylsiloxy)propene, a neutral π-nucleophile, was found to be able to efficiently catalyze the cyanation (cyanosilylation and cyanocarbonation) of various aldehydes and ketones, and this study provided the first illustration of u
- Wang, Xiu,Tian, Shi-Kai
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p. 1416 - 1420
(2008/03/11)
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- Highly efficient trialkylsilylcyanation of aldehydes, ketones and imines catalyzed by a nucleophilic N-heterocyclic carbene
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The synthetic utility of N-heterocyclic carbenes was demonstrated by the trialkylsilylcyanation of aldehydes, ketones and imines. In the presence of a catalytic amount of 3a, the reactions with Me3SiCN proceeded smoothly to give the corresponding cyanohydrin trimethylsilyl ethers or amino nitrile derivatives in good to excellent yields.
- Kano, Taichi,Sasaki, Kouji,Konishi, Teppei,Mii, Haruka,Maruoka, Keiji
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p. 4615 - 4618
(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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- Dodecatungestophosphoric acid (H3PW12O40) as a solid green Br?nsted acid catalyzes high yielding and efficient trimethylcyanosylilation reactions of aldehydes and ketones by trimethylsilyl cyanide
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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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- Solvent-free synthesis of cyanohydrin derivatives catalysed by triethylamine
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A very simple one-step environmentally friendly procedure for the synthesis of O-substituted cyanohydrins from aldehydes and ketones, in the absence of solvent, employing minimum amounts of the corresponding cyanides has been optimised. Aldehydes react more rapidly than ketones using triethylamine as catalyst offering in both cases almost quantitative yields of the corresponding O-trimethylsilyl, O-methoxycarbonyl, O-benzoyl and O-acetyl cyanohydrins. Georg Thieme Verlag Stuttgart.
- Baeza, Alejandro,Najera, Carmen,Retamosa, Ma. De Gracia,Sansano, Jose M.
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p. 2787 - 2797
(2007/10/03)
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- Inorganic/organic salts as heterogeneous basic catalysts for cyanosilylation of carbonyl compounds
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The addition of TMSCN to carbonyl compounds catalyzed by K 2CO3 as heterogeneous catalyst gave the corresponding cyanohydrin trimethylsilyl ethers from 20 minutes to 24 hours with 62% to 99% yields without solvent at room temperature
- He, Bin,Li, Yan,Feng, Xiaoming,Zhang, Guolin
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p. 1776 - 1778
(2007/10/03)
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- Effective activation of the chiral salen/Ti(OiPr)4 catalyst with achiral phenolic N-oxides as additives in the enantioselective cyanosilylation of ketones
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The activation of chiral titanium(IV) complexes with phenolic N-oxides additives has been found to provide an alternative strategy for the asymmetric cyanosilylation of ketones. By using 10 mol % of chiral salen-titanium(IV) complex in combination with 1
- He, Bin,Chen, Fu-Xue,Li, Yan,Feng, Xiaoming,Zhang, Guolin
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p. 4657 - 4666
(2007/10/03)
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- Highly efficient double-activation catalysts for the synthesis of ketone cyanohydrins
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Tertiary cyanohydrin trimethylsilyl ethers were synthesized in excellent chemical yields by using salen-Al complex (0.25 mol%) and N-oxide (0.5 mol%) without solvent at ambient temperature. The relationship between the ligand structure and catalyst effici
- Chen, Fu-Xue,Liu, Xiaohua,Qin, Bo,Zhou, Hui,Feng, Xiaoming,Zhang, Guolin
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p. 2266 - 2272
(2007/10/03)
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- Highly Efficient Silylcyanation of Ketones by a Catalytic Double Activation Method Using Lewis Acid and N-Oxide Catalysts
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An efficient protocol for addition of TMSCN to ketones by employing 3 mol percent achiral Schiff base-Ti(IV) complex as the Lewis acid and 3 mol percent N-oxide as the Lewis base in a manner of double activation was described. Aromatic, aliphatic, cyclic,
- Chen, Fuxue,Feng, Xiaoming,Qin, Bo,Zhang, Guolin,Jiang, Yaozhong
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p. 558 - 560
(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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- 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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- Trimethylsilyl Cyanide - A Reagent for Umpolung, XI. On the Ambident Character of Substituted Allylic Anions.
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The dependence of the α/γ-ratio of alkylation products on several factors has been determined with 1-cyano-3-aryl-1-(trimethylsiloxy)allylic anions.Increasing amounts of γ-product are found in more polar solvents, with larger alkali ions, on addition of HMPT, with smaller alkyl groups in the electrophile, and especially with p-cyanophenyl groups.In contrast, temperature and leaving groups have minor effects.On substitution of the O-silyl group by O-methyl and O-ethoxycarbonyl, α-alkylation predominates strongly.The results are compared to known allylic anions.Furthermore, the isomerisation of compounds of type C to type B is described as well as a new addition reaction of cyanoformates to aldehydes.
- Huenig, Siegfried,Reichelt, Helmut
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p. 1772 - 1800
(2007/10/02)
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- Trimethylsilyl Cyanide - A Reagent for Umpolung, X. α,β-Unsaturated Carbonyl Compounds from Saturated Carboxylic Acids by Redox Umpolung
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2-(Trimethylsiloxy)acrylonitriles C, easily available from acyl chlorides A, can be deprotonated to the ambident anions E.These are attacked by alkylating agents in α-position mainly with formation of G which finally is transformed to I (Scheme 1).Deproto
- Hertenstein, Ulrich,Huenig, Siegfried,Reichelt, Helmut,Schaller, Rainer
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p. 722 - 728
(2007/10/02)
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- A Simple One-Pot Synthesis of Silylated and Acylated Cyanohydrins
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Reaction of variety of aldehydes and ketones with chlorotrimethylsilane and acyl chlorides in the presence of lithium cyanide to give trimethylsilylcyanohydrins and acylcyanohydrins is described.
- Yoneda, Ryuji,Santo, Kazunori,Harusawa, Shinya,Kurihara, Takushi
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p. 1054 - 1055
(2007/10/02)
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- Trimethylsilyl Cyanide - A Reagent for Umpolung, V. Nucleophilic Acylation of Alkylating Reagents with α,β-Unsaturated Aldehydes.
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The readily accessible adducts 3 from α,β-unsaturated aldehydes and trimethylsilyl cyanide react smoothly after deprotonation (LDA) as anions 3A with different alkylating agents in 1-position.Removal of the protective group under mild conditions yields the α,β-unsaturated ketones 5 in 60 - 80 percent overall yield.The stability of anions 3A is increased by an O-triethylsilyl group.Alkylation of 3A in 3-position (partly) is caused by 3-acceptor substituents.Nucleophilic acylation with α-alkoxyaldehydes produces 1,2-diketones via a new route.
- Hertenstein, Ulrich,Huenig, Siegfried,Oeller, Manfred
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p. 3783 - 3802
(2007/10/02)
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