Reaction Of Trimethylsilyl Cyanide Research Articles

A Concise Synthesis of 2‐(2‐Hydroxyphenyl)acetonitriles via the o‐Quinone Methides Generated from 2‐(1‐Tosylalkyl)phenols

AbstractA concise synthesis of 2‐(2‐hydroxyphenyl)acetonitriles has been developed through reaction of trimethylsilyl cyanide and the o‐quinone methides in situ generated from 2‐(1‐tosylalkyl)phenols under basic conditions. In addition, 2‐(2‐hydroxyphenyl)acetonitriles could be conveniently transformed to benzofuranones.

Synthesis of metallasiloxanes of group 13–15 and their application in catalysis

Herein we report on the synthesis, characterization and catalytic application of metallasiloxanes of group 13-15. Reactions of R(Me)Si(OH)2 (R = N(SiMe3)-2,6-iPr2C6H3) (A) with Bi(NEt2)3, Sb(NEt2)3, Ge[N(SiMe3)2]2 and AlMe3 afforded [R(Me)SiO2BiNEt2]2 (1), [R(Me)SiO2SbOSi(OH)(Me)R]2 (2), [R(Me)SiO2]3(GeH)2 (3), and [R(Me)SiO2AlMe(THF)]2 (4), respectively. Reactions of RSi(OH)3 (B) with Bi(NEt2)3 and AlMe3 produced complexes (RSiO3Bi)4 (5) and (RSiO3)2[AlMe(THF)]3 (6). Compounds 1-6 have been characterized by IR and NMR spectroscopy, single crystal X-ray structure and elemental analysis. Each of the compounds 1, 2 and 4 features an eight-membered ring of composition Si2O4Bi2, Si2O4Sb2 and Si2O4Al2, while 3 and 6 exhibit a bicyclic structure with the respective skeletons of Si3O6Ge2 and Si2O6Al3. Compound 5 has a cubic core of Si4O12Bi4. Compounds 1-6 exhibit very good catalytic activity in the addition reaction of trimethylsilyl cyanide (TMSCN) with benzaldehyde. Compound 5 was found to be the best catalyst and its activity was probed in the reactions of TMSCN with a number of aldehydes and ketones.

Boric Acid Catalysed Synthesis of α-Aminonitriles by a Three-Component Reaction at Room Temperature

A simple, efficient, and cost-effective method has been developed for the one-pot, three-component condensation reaction of trimethylsilyl cyanide, aldehydes and aromatic amines using boric acid as a heterogeneous solid acid catalyst, under solvent-free conditions. α-Aminonitriles were synthesised relatively quickly in good yields at room temperature.

Solvent‐free cyanosilylation of aldehydes catalyzed by SmI2

AbstractA novel method to obtain racemic cyanohydrin silylethers by reaction of trimethylsilyl cyanide with a variety of aldehydes promoted by catalysis of SmI2 is reported. The corresponding cyanosilylethers were obtained in high yields (up to 99%) in solvent‐ free conditions at room temperature within a relatively short time using 0.01–0.5 mol% catalyst loadings. Copyright © 2007 John Wiley & Sons, Ltd.

Nucleophilic Additions of Trimethylsilyl Cyanide to Cyclic Oxocarbenium Ions: Evidence for the Loss of Stereoselectivity at the Limits of Diffusion Control

The limitations of stereoelectronic models in assessing the stereoselective nucleophilic substitution reactions of cyclic oxocarbenium ions at high reaction rates are discussed. Evidence is provided suggesting that the diastereoselectivity of nucleophilic substitution reactions is attenuated at the limits of diffusion control. The low diastereoselectivities observed in the reactions of trimethylsilyl cyanide with five- and six-membered ring oxocarbenium ions are attributed to the high reactivity of the nucleophile and its reactions with these electrophiles at diffusion control rates.

Multicomponent Cascade Reactions: Sequential [1 + 4] and [2 + 3] Cycloadditions for the Generation of Heterocyclic Ring Systems.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Multicomponent Cascade Reactions: Sequential [1 + 4] and [2 + 3] Cycloadditions for the Generation of Heterocyclic Ring Systems

[reaction: see text]. A novel intermolecular nitrile oxide cycloaddition sequence has been developed for the formation of highly substituted heterocyclic rings. Reaction of trimethylsilyl cyanide with epoxides generates isonitriles which can react with nitroalkenes to form N-(isoxazolylidene)alkylamines. After fragmentation to nitrile oxides, the dipoles can undergo intermolecular 1,3-dipolar cycloadditions with electron deficient dipolarophiles to generate substituted isoxazolines in one synthetic operation.

An Improved Synthesis of Cyanohydrins in the Presence of Solid LiClO4 under Solvent‐Free Conditions.

AbstractFor Abstract see ChemInform Abstract in Full Text.

An improved synthesis of cyanohydrins in the presence of solid LiClO 4 under solvent-free conditions

Several cyanohydrins were synthesized by the reaction of trimethylsilyl cyanide with carbonyl compounds in the presence of solid lithium perchlorate in high yields under solvent-free conditions.

Trimethylsilyl Cyanide Addition to Carbonyl Compounds Under Neutral Condition Catalyzed by Iodine

Reaction of trimethylsilyl cyanide with aliphatic or aromatic aldehydes and ketones in the presence of a catalytic amount of elemental iodine produced the corresponding cyanohydrin trimethylsilyl ethers in very short time and high yields.

Cyanation of nucleophilic alkynes: easy approach to element-substituted α-cyanoenamines

The reactions of trimethylsilyl cyanide and tributyltin cyanide with ynamines proceeds as a regioselective syn-addition and provide previously unknown β-elementosubstituted α-cyanoenamines as pure E-isomers. The reaction of cyanogen bromide with ynamines as well the hydrocyanation of phosphorus substituted N,N-diethylaminoacetylenes by acetone cyanohydrin also proceeds as regioselective syn-addition, though the initially formed Z-isomers undergo an easy transformation into E-isomers. Cross-coupling reaction of β-bromo-α-cyanoenamine with arylboronic acids were shown to be an easy and convenient approach to α-dialkylaminosubstituted cynnamonitriles.

ChemInform Abstract: Regioselective Addition of Trimethylsilyl Cyanide to β-Alkoxyvinyl Alkyl Ketones.

Abstract The 1,2- and 1.4-addition reactions of trimethylsilyl cyanide to alkyl vinyl ketones were studied. Regioselectivity of this reaction depends on the structure of alkyl vinyl ketones, the reaction temperature and the nature of catalyst. The presence of alkoxy group in β-position of α,β-enone is the important condition for realization of 1,4-addition. Ambient temperature (25°C) or base catalyst (NEt3) directed the reaction predominantly into 1,2-addition; higher temperature, electrophilic catalyst (I2) and bulky alkyl substituents near the carbonyl group directed the reaction in 1,4-addition route. Hydrolysis of 1,4-adducts yields saturated fluorine-containing ketones containing CN- and ethoxy groups at the β-position.

A catalytic asymmetric strecker-type reaction promoted by Lewis acid-Lewis base bifunctional catalyst.

A general asymmetric Strecker-type reaction is reported, catalyzed by the Lewis acid-Lewis base bifunctional catalyst 1. The reaction of trimethylsilyl cyanide (TMSCN) with various fluorenyl imines, including n-aldimines and alpha,beta-unsaturated imines, proceeds with good to excellent enantioselectivities in the presence of a catalytic amount of phenol as additive (20 mol%) (catalytic system 1). The products were successfully converted to the corresponding amino acid derivatives in high yields without loss of enantiomeric purity. Furthermore, hydrogenation or dihydroxylation of the products from alpha,beta-unsaturated imines afforded saturated or functionalized aminonitriles also without loss of enantiomeric purity. The absolute configuration of the products and a control experiment using catalyst 2 supported the proposed dual activation of the imine and TMSCN by the Lewis acid (Al) and the Lewis base moiety (phosphine oxide) of 1. From the mechanistic studies including kinetic and NMR experiments of the catalytic species, the role of PhOH seems to be a proton source to protonate the anionic nitrogen of the intermediate. Specifically, we have found that TMSCN is more reactive than HCN in this catalytic system, probably due to the activation ability of the phosphine oxide moiety of 1 toward TMSCN. This fact prompted us to develop the novel catalytic system 2, consisting of 1 (9 mol%), TMSCN (20 mol%) and HCN (1.2 mol eq). This new system afforded comparable results with obtained by system 1 (1 (9 mol%)-TMSCN (2 mol eq)-PhOH (20 mol%)).

The reactions of trimethylsilylcyanide with titanium (IV) halides

Abstract Reaction of trimethylsilylcyanide with titanium (IV) chloride occurs readily at room temperature. Mono-adduct formation occurs initially, followed by substitution of chloride by cyanide under more forcing conditions. By choosing appropriate reaction conditions, it has been possible to isolate a series of products of composition, TiCl4−n(CNn · (CH3)3SiCN (n = 0, 1, 2, 3). The products are believed to possess dimeric (n = 0, 1) or polymeric (n = 2, 3) structures, containing approximately octahedrally coordinated titanium atoms. Attempts to remove the coordinated molecules from these products by thermal decomposition have proved unsuccessful, although adducts of composition TiCl2(CN)2·(CH3CN)1.5 and TiCl2(CN)2·(CH3CN)0.5 have been produced from ligand exchange reactions with acetonitrile. The titanium (IV) bromide analogue of the unsubstituted adduct, i.e. [TiBr4·(CH3)3SiCN]2, has also been isolated but attempts to produce substituted titanium-cyanide complexes from titanium (IV) bromide or titanium (IV) iodide yield intractable mixtures of products.

ChemInform Abstract: A New Method for the Construction of the Pyrrole Ring by the Carbonylcobalt‐Catalyzed Reaction of Trimethylsilyl Cyanide with Acetylenes. Its Scope and Limitations.

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ChemInform Abstract: Facile Synthesis of Thiocyanate Using Trimethylsilyl Cyanide.

Arenethiocyanate can be prepared by reaction of trimethylsilyl cyanide with sodium arenesulphinate or arenesulphonyl chloride.

ChemInform Abstract: Me3SiCN. Part 6. Palladium‐ and Nickel‐Catalyzed Reaction of Trimethylsilyl Cyanide with Acetylenes. Addition of Trimethylsilyl Cyanide to the Carbon‐Carbon Triple Bonds.

AbstractReaction of trimethylsilyl cyanide (II) with the arylacetylenes (I) in the presence of various transition‐metal complexes yields the cyano‐substituted vinylsilanes (III) with a high regio‐ and stereoselectivity.

An unexpected ring-opening in the reissert reaction on 2,3-diphenylquinoxaline-n-oxide.

When quinoxaline-N-oxide 1 is reacted with KCN and benzoyl chloride in water (the Reissert reaction) or methanol, the products are 2-,5- and 6- chloroquinoxaline (the latter being the major product: 42±6 %) and small amounts of 2-cyanoquinoxaline. Using three equivalents of trimethylsilyl cyanide instead of KCN, and dichloromethane as the solvent, leads to a 72 % yield of 2-cyanoquinoxaline. The reaction of trimethylsilyl cyanide and benzoyl chloride with 2,3-diphenylquinoxaline-N-oxide 2 leads to an unexpected ring-opening product 13; its structure is based on spectroscopic data and on an X-ray crystallographic analysis.

Facile synthesis of thiocyanate using trimethylsilyl cyanide

Arenethiocyanate can be prepared by reaction of trimethylsilyl cyanide with sodium arenesulphinate or arenesulphonyl chloride.

Transition-metal-catalyzed reactions of trimethylsilyl cyanide. 4. Palladium-catalyzed cyanation of aryl halides by trimethylsilyl cyanide

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTTransition-metal-catalyzed reactions of trimethylsilyl cyanide. 4. Palladium-catalyzed cyanation of aryl halides by trimethylsilyl cyanideNaoto Chatani and Terukiyo HanafusaCite this: J. Org. Chem. 1986, 51, 24, 4714–4716Publication Date (Print):November 1, 1986Publication History Published online1 May 2002Published inissue 1 November 1986https://doi.org/10.1021/jo00374a041RIGHTS & PERMISSIONSArticle Views1299Altmetric-Citations116LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (440 KB) Get e-Alerts Get e-Alerts