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Trimethylsilyl Cyanide (trimethylsilyl + cyanide)
Selected AbstractsSynthesis of ,-Amino Nitriles from Carbonyl Compounds, Amines, and Trimethylsilyl Cyanide: Comparison between Catalyst-Free Conditions and the Presence of Tin Ion-Exchanged MontmorilloniteEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 9 2010Jiacheng Wang Abstract In the absence of catalysts, the three-component, one-pot synthesis of ,-amino nitriles proceeded using various aldehydes and ketones together with amines and trimethylsilyl cyanide (TMSCN) in high yields under neat conditions at room temperature. The addition order of the reagents had a significant influence on the yields of the desired ,-amino nitriles. In contrast, when tin ion-exchanged montmorillonite (Sn-Mont), prepared by the ion-exchange of sodium montmorillonite (Na-Mont) with a tin tetrachloride solution, was used as a catalyst, the reaction rates significantly increased compared with those without catalysts, and the range of the applicable carbonyl compounds was also extended: structurally diverse aromatic, aliphatic and heteroatom-containing carbonyl compounds, including sterically hindered ketones as well as aliphatic and aromatic amines, were converted into the desired ,-amino nitriles in good to excellent yields with short reaction times under mild conditions. Sn-Mont showed a better catalytic activity than proton or other metal ion-exchanged montmorillonites, supported SnO2 catalysts and the previously reported homogeneous or heterogeneous catalysts. The recovered catalyst was reused several times without loss of catalytic performance. Along with the expansion of the interlayer space of Sn-Mont, the strong Brønsted acid and Lewis acid nature of Sn-Mont derived from protons and SnO2 nanoparticles present in the interlayers of Sn-Mont likely played important and cooperative roles in the high catalytic activity. [source] Asymmetric meso -Epoxide Ring-Opening with Trimethylsilyl Cyanide Promoted by Chiral Binuclear Complexes of Titanium.ADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 18 2009Dichotomy of CC versus CN Bond Formation Abstract In the presence of chiral catalysts derived from the same chiral hexadentate ligand and aluminium, zinc or titanium ions, the reaction between cyclohexene oxide and trimethylsilyl cyanide can be controlled to give predominantly either the nitrile (up to 99% ee) or the isonitrile product (up to 94% ee). The metal ion, ligand stereochemistry and base concentration all play a role in determining the product ratio. [source] ChemInform Abstract: Synthesis of N-Allylideneamines and Their Use for the Double Nucleophilic Addition of Ketene Silyl (Thio)acetals and Trimethylsilyl Cyanide.CHEMINFORM, Issue 4 2009Isao Mizota Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] ChemInform Abstract: Niobium(V) Chloride Catalyzed Synthesis of ,-Aminonitriles with Simultaneous Reaction of Aldehydes, Amines and Trimethylsilyl Cyanide.CHEMINFORM, Issue 47 2008Anjoy Majhi Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] ChemInform Abstract: Tetraaryl-1,3-dioxolane-4,5-dimethanols as Catalysts for the Addition of Trimethylsilyl Cyanide to Benzaldehyde and the Oxirane Ring.CHEMINFORM, Issue 22 2008Yu. N. Belokon Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] Asymmetric Addition of Trimethylsilyl Cyanide to Ketones Catalyzed by Al(salen)/triphenylphosphine Oxide.CHEMINFORM, Issue 17 2006Sung Soo Kim Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF. [source] Enantioselective Addition of Trimethylsilyl Cyanide to Aldehydes Catalyzed by Bifunctional BINOLAM-AlCl versus Monofunctional BINOL-AlCl Complexes.CHEMINFORM, Issue 9 2005Jesus Casas Abstract For Abstract see ChemInform Abstract in Full Text. [source] Enantioselective Strecker Reactions Between Aldimines and Trimethylsilyl Cyanide Promoted by Chiral N,N,-Dioxides.CHEMINFORM, Issue 5 2004Zhigang Jiao Abstract For Abstract see ChemInform Abstract in Full Text. [source] Double Nucleophilic Addition of Ketene Silyl (Thio)acetals and Trimethylsilyl Cyanide to ,,,-Unsaturated Aldimines Promoted by Aluminum Chloride.CHEMINFORM, Issue 45 2003Makoto Shimizu Abstract For Abstract see ChemInform Abstract in Full Text. [source] Synthesis of ,-Amino Nitriles from Carbonyl Compounds, Amines, and Trimethylsilyl Cyanide: Comparison between Catalyst-Free Conditions and the Presence of Tin Ion-Exchanged MontmorilloniteEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 9 2010Jiacheng Wang Abstract In the absence of catalysts, the three-component, one-pot synthesis of ,-amino nitriles proceeded using various aldehydes and ketones together with amines and trimethylsilyl cyanide (TMSCN) in high yields under neat conditions at room temperature. The addition order of the reagents had a significant influence on the yields of the desired ,-amino nitriles. In contrast, when tin ion-exchanged montmorillonite (Sn-Mont), prepared by the ion-exchange of sodium montmorillonite (Na-Mont) with a tin tetrachloride solution, was used as a catalyst, the reaction rates significantly increased compared with those without catalysts, and the range of the applicable carbonyl compounds was also extended: structurally diverse aromatic, aliphatic and heteroatom-containing carbonyl compounds, including sterically hindered ketones as well as aliphatic and aromatic amines, were converted into the desired ,-amino nitriles in good to excellent yields with short reaction times under mild conditions. Sn-Mont showed a better catalytic activity than proton or other metal ion-exchanged montmorillonites, supported SnO2 catalysts and the previously reported homogeneous or heterogeneous catalysts. The recovered catalyst was reused several times without loss of catalytic performance. Along with the expansion of the interlayer space of Sn-Mont, the strong Brønsted acid and Lewis acid nature of Sn-Mont derived from protons and SnO2 nanoparticles present in the interlayers of Sn-Mont likely played important and cooperative roles in the high catalytic activity. [source] One-Pot Three-Component Synthesis of , -Amino Nitriles Catalyzed by 2,4,6-Trichloro-1,3,5-triazine (Cyanuric Acid),HELVETICA CHIMICA ACTA, Issue 6 2007Biswanath Das Abstract A simple and efficient method has been developed for the synthesis of , -amino nitriles from aldehydes, amines and trimethylsilyl cyanide (Me3SiCN) in the presence of a catalytic amount of cyanuric acid at room temperature. [source] Asymmetric meso -Epoxide Ring-Opening with Trimethylsilyl Cyanide Promoted by Chiral Binuclear Complexes of Titanium.ADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 18 2009Dichotomy of CC versus CN Bond Formation Abstract In the presence of chiral catalysts derived from the same chiral hexadentate ligand and aluminium, zinc or titanium ions, the reaction between cyclohexene oxide and trimethylsilyl cyanide can be controlled to give predominantly either the nitrile (up to 99% ee) or the isonitrile product (up to 94% ee). The metal ion, ligand stereochemistry and base concentration all play a role in determining the product ratio. [source] Catalytic 1,2-Dicyanation of Alkynes by Palladium(II) under Aerobic ConditionsADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 11-12 2009Shigeru Arai Abstract A stereoselective 1,2-dicyanation of various alkynes in the presence of trimethylsilyl cyanide (TMSCN) by palladium(II) catalysis under aerobic conditions is investigated. This reaction includes two cyanation pathways, syn - and anti -cyanopalladation to alkynes that are activated by Pd(II). High syn -selectivity was observed in the reaction using terminal alkynes that have bulky substituents at a propargyl position and aliphatic internal alkynes. Furthermore, a dramatic acceleration was observed with substrates having an N -arenesulfonyl functionality at a propargyl position, this indicates that both sulfoxide and carbon-carbon triple bond act as Lewis bases to Pd(II). [source] Gold(III) Chloride-Catalyzed Diastereoselective Alkylation Reactions with Chiral Benzylic AcetatesADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 7-8 2008Philipp Rubenbauer Abstract Gold(III) chloride was shown to be an efficient catalyst for the diastereoselective CC bond formation of various chiral para -methoxybenzylic acetates and different nucleophiles. All electrophilic acetates carried next to the reacting center a stereogenic carbon center bound to a functional group (FG), a methyl substituent and a proton. Selectivities were good (dr>80/20) in favor of the anti -product for FG=COOMe, NO2, CN and in favor of the syn -product for FG=SO2Et, PO(OEt)2. The reactions proceed most likely via a free carbocation, in which a face differentation is facilitated by a preferred conformation. Several arene nucleophiles were shown to be compatible with the catalysis conditions providing the corresponding substitution products in high yields (13 examples, 62,98%). Moreover, other nucleophiles (allyltrimethylsilane, trimethylsilyl cyanide, 2,2-dimethyl-3-(trimethylsilyloxy)butane, p -toluenesulfonamide, and acetylacetone) reacted with a representative chiral electrophile in a high yielding and diastereoselective fashion. [source] Enantioselective Cyanosilylation of Ketones Catalyzed by a Nitrogen-Containing Bifunctional CatalystADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 4-5 2006Yan Xiong Abstract An efficient and optically active, bifunctional tetraaza ligand (2S)- N -{(1R,2R)-2-[(S)-pyrrolidine-2-carboxamido]-1,2-diphenylethyl}pyrrolidine-2-carboxamide has been developed for the addition of trimethylsilyl cyanide (TMSCN) to ketones. The bifunctional catalyst system based on a monometallic titanium complex was found to be a highly enantioselective catalyst to provide O -TMS cyanohydrins with up to 94% ee. A possible transition state has been proposed to explain the origin of the activation and asymmetric inductivity. [source] Organocatalytic synthesis of cyanohydrin trimethylsilyl ethers by potassium 4-benzylpiperidinedithiocarbamate under solvent-free conditionsAPPLIED ORGANOMETALLIC CHEMISTRY, Issue 3 2010Mohammad G. Dekamin Abstract 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 quantitative yields. The reaction proceeded smoothly by employing 2.0 mol% PBPDC loading under mild conditions at room temperature within a very short reaction time. Copyright © 2009 John Wiley & Sons, Ltd. [source] Solvent-free synthesis of , -aminonitriles from aldehydes, amines and trimethylsilyl cyanide catalyzed by thallium(III) chloride tetrahydrateAPPLIED ORGANOMETALLIC CHEMISTRY, Issue 12 2008Anjoy Majhi Abstract A straightforward and efficient method has been developed for the synthesis of ,-aminonitriles by combining aldehydes, amines and trimethylsilyl cyanide in the presence of a catalytic amount of thallium(III) chloride tetrahydrate (1 mol%) under solvent-free conditions at room temperature. Copyright © 2008 John Wiley & Sons, Ltd. [source] Nucleophilic Cyclopropanation Reaction with Bis(iodozincio)methane by 1,4-Addition to ,,,-Unsaturated Carbonyl CompoundsCHEMISTRY - AN ASIAN JOURNAL, Issue 8 2009Kenichi Nomura Abstract Treatment of ,,,-unsaturated ketones with an electrophilic site at the ,-position in the presence of trimethylsilyl cyanide with bis(iodozincio)methane afforded the (Z)-silyl enol ether of the ,-cyclopropyl substituted ketone in good yields. The reaction proceeds by 1,4-addition to form an enolate, and its sequential intramolecular nucleophilic attack to an adjacent electrophilic site. The reaction of ,-ethoxycarbonyl-,,,-unsaturated ketone and bis(iodozincio)methane in the presence of trimethylsilyl cyanide afforded 1-ethoxy-1-trimethylsiloxycyclopropane derivatives, which can be regarded as the homoenolate equivalent. Additionally, reaction of the obtained homoenolate equivalents with imines give 1-(E)-alkenyl-2-(1-aminoalkyl)alkanols diastereoselectively. [source] | ||||||||||||||||||||||