Presence Of Trimethylsilyl Cyanide Research Articles

Three-Component Synthesis of Multiple Functionalized Allenes via Copper/Photoredox Dual Catalyzed 1,4-Alkylcyanation of 1,3-Enynes.

Efficient access to multiple functionalized allenes via a three component 1,4-alkylcyanation of enynes with cyclic alcohol derivatives in the presence of trimethylsilyl cyanide (TMSCN) under copper/photoredox dual catalysis has been developed. Both easily transformable aldehyde and cyano groups were introduced to tetra-substituted allenes through light-induced C-C bond cleavage of cyclic butanol and pentanol derivatives. The reactions proceeded smoothly under mild conditions with broad functional groups tolerance.

Polyaromatic Group Embedded Cd(II)-Coordination Polymers for Microwave-Assisted Solvent-Free Strecker-Type Cyanation of Acetals.

In this work, two new 1D Cd(II) coordination polymers (CPs), [Cd(L1)(NMF)2]n (1) and [Cd(L2)(DMF)(H2O)2]n·n(H2O) (2), have been synthesized, characterized and employed as catalysts for the microwave-assisted solvent-free Strecker-type cyanation of different acetals. Solvothermal reaction between the pro-ligand, 5-{(pyren-1-ylmethyl)amino}isophthalic acid (H2L1) or 5-{(anthracen-9-ylmethyl)amino}isophthalic acid (H2L2), and Cd(NO3)2.6H2O in the presence of NMF or DMF:THF solvent, produces the coordination polymer 1 or 2, respectively. These frameworks were characterized by single-crystal and powder X-ray diffraction analyses, ATR-FTIR, elemental and thermogravimetry analysis. Their structural analysis revealed that both CPs show one-dimensional structures, but CP 1 has a 1D double chain type structure whereas CP 2 is a simple one-dimensional network. In CP 1, the dinuclear {Cd2(COO)4} unit acts as a secondary building unit (SBU) and the assembly of dinuclear SBUs with deprotonated ligand (L12-) led to the formation of a 1D double chain framework. In contrast, no SBU was observed in CP 2. To test the catalytic effectiveness of these 1D compounds, the solvent-free Strecker-type cyanation reactions of different acetals in presence of trimethylsilyl cyanide (TMSCN) was studied with CPs 1 and 2 as heterogenous catalysts. CP 1 displays a higher activity (yield 95%) compared to CP 2 (yield 84%) after the same reaction time. This is accounted for by the strong hydrogen bonding packing network in CP 2 that hampers the accessibility of the metal centers, and the presence of the dinuclear Cd(II) SBU in CP 1 which can promote the catalytic process in comparison with the mononuclear Cd(II) center in CP 2. Moreover, the recyclability and heterogeneity of both CPs were tested, demonstrating that they can be recyclable for at least for four cycles without losing their structural integrity and catalytic activity.

Lewis Acid-Catalyzed Diastereoselective Domino Reaction of Ene-Ynamide with Trimethylsilyl Cyanide to Construct Spiroindolines.

The Zn(OTf)2-catalyzed domino reaction of enamide-ynamides in the presence of trimethylsilyl cyanide as an external nucleophile to construct spirocyclic indolines was developed. This domino reaction involved cyclization of enamide to ynamide to generate 4',5'-dihydrospiro[indoline-3,3'-pyrrol]-1'-ium followed by cyanide addition to produce spiroindolopyrrolidines with good diastereoselectivity.

Catalytic 1,2‐Dicyanation of Alkynes by Palladium(II) under Aerobic Conditions

AbstractA 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).

Palladium(II)‐Mediated Nucleophilic Cyanation of 4‐Substituted Quinoline 1‐Oxide in the Presence of Trimethylsilyl Cyanide and an Oxidant.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Palladium(II)-mediated Nucleo- philic Cyanation of 4-Substituted Quinoline 1-Oxide in the Presence of Trimethylsilyl Cyanide and an Oxidant

Reaction of 4-substituted (electron-releasing group) quinoline 1-oxides (1) with trimethylsilyl cyanide in the presence of palladium(II) acetate and DDQ gave 2-cyano-4-substituted quinoline 1-oxides (2) in THF in moderateyields. It was reasoned that this reaction proceeds through palladium-catalyzed dehydrosilylation.

ChemInform Abstract: Single Electron Transfer Photoinduced Oxidation of Piperidine and Pyrrolidine Derivatives to the Corresponding Lactams.

Irradiation by visible light of various N-arylaminopiperidines or N-arylaminopyrrolidines in presence of a catalytic amount of photosensitizer led with good yields to the corresponding N-arylaminolactams under mild conditions. This reaction proceeds by two consecutive photooxidations, the first in presence of trimethylsilyl cyanide and the second one in presence of water. Voltammetric investigations demonstrated clearly that hydrazines are more readily oxidised than tertiary amines, and as a consequence it is possible to obtain by photooxidation a wider range of oxidised compounds.

Single electron transfer photoinduced oxidation of piperidine and pyrrolidine derivatives to the corresponding lactams

Irradiation by visible light of various N-arylaminopiperidines or N-arylaminopyrrolidines in presence of a catalytic amount of photosensitizer led with good yields to the corresponding N-arylaminolactams under mild conditions. This reaction proceeds by two consecutive photooxidations, the first in presence of trimethylsilyl cyanide and the second one in presence of water. Voltammetric investigations demonstrated clearly that hydrazines are more readily oxidised than tertiary amines, and as a consequence it is possible to obtain by photooxidation a wider range of oxidised compounds.

Homoconjugate Addition of Organocuprate to Activated Cyclopropane and Its Application to the Synthesis of (±)-Juvabione

The homoconjugate addition of various organocopper reagents to doubly activated cyclopropane (1) was investigated. The otpimized yield (81 %) was obtained when using higher-order cyano cuprate in the presence of trimethylsilyl cyanide, and the reaction was applied to synthesize (±)-juvabione intermediate 9.

Attempted Polymerization of Benzimidazole via Reissert Reactions

Approaches to benzimidazole polymerization using Reissert compound chemistry are described. Poly(benzimidazole Reissert compound)s in which both nitrogen atoms are part of amide linkages and a cyano group is present at the 2-position of the benzimidazole ring were prepared from benzimidazole itself or bi(1-benzimidazyl)adipoyl by reaction with diacid chlorides in the presence of trimethylsilyl cyanide; however, low molecular weight resulted under a variety of conditions. Attempts to synthesize polyethers by condensation of the new Reissert compound 1,3-bis(p-fluorobenzoyl)-2-cyano-2,3-dihydrobenzimidazole and bisphenol A failed due to hydrolysis of the Reissert compound under the reaction conditions

ChemInform Abstract: Photoinduced Reactions. Part 168. Photooxygenation of Furans in the Presence of Trimethylsilyl Cyanide.

AbstractAus den Furanen (I) erhält man bei der Photooxidation und Behandlung mit Dimethylsulfid die Diketone (II), die mit Trimethylsilylcyanid zu den Dihydrofuranen (III) recyclisiert werden.

Photooxygenation of furans in the presence of trimethylsilyl cyanide. Oxidative cyanation of furans

Low-temperature photooxygenation of furan derivatives followed by treatment with dimethyl sulfide and trimethylsilyl cyanide provides 2-cyano-5-hydroxy-2,5-dihydrofurans which are converted to 4-cyanobutenolides.