4354-72-7

Upstream product

• 53535-83-4 B-cyclohexyl-9-borabicyclo<3.3.1>nonane 
• 1885-22-9 bromomalononitrile 
• 4354-73-8 2-(cyclohexylidene)malononitrile 
• 110-83-8 cyclohexene 
• 108-94-1 cyclohexanone 
• 109-77-3 malononitrile 
• 762-72-1 allyl-trimethyl-silane 

Downstream Products

• 1244024-61-0 C₂₆H₂₇N₃O₅ 
• 1244024-85-8 C₂₆H₂₆FN₃O₅ 
• 1244024-86-9 C₂₆H₂₆ClN₃O₅ 
• 1244024-87-0 C₂₇H₂₉N₃O₆ 
• 22733-94-4 benzyl cyclohexanecarboxylate 
• 645-59-0 dihydrocinnamonitrile 
• 1823-91-2 1-phenylethyl cyanide 

Relevant academic research and scientific papers

Overcoming Selectivity Issues in Reversible Catalysis: A Transfer Hydrocyanation Exhibiting High Kinetic Control

Reversible catalytic reactions operate under thermodynamic control, and thus, establishing a selective catalytic system poses a considerable challenge. Herein, we report a reversible transfer hydrocyanation protocol that exhibits high selectivity for the thermodynamically less favorable branched isomer. Selectivity is achieved by exploiting the lower barrier for C-CN oxidative addition and reductive elimination at benzylic positions in the absence of a cocatalytic Lewis acid. Through the design of a novel type of HCN donor, a practical, branched-selective, HCN-free transfer hydrocyanation was realized. The synthetically useful resolution of a mixture of branched and linear nitrile isomers was also demonstrated to underline the value of reversible and selective transfer reactions. In a broader context, this work demonstrates that high kinetic selectivity can be achieved in reversible transfer reactions, thus opening new horizons for their synthetic applications.

One methyl group makes a major difference: Shape-selective catalysis by zeolite nanoreactors in liquid-phase condensation reactions

The precise sizes of zeolites' micropores can induce sharp shape/size-selectivity with precision of less than 1 ? in gas-phase reactions, e.g. methanol to olefin reactions (MTO). However, it is still a major challenge and an unachieved task in liquid-phas

Sterically Demanding Oxidative Amidation of α-Substituted Malononitriles with Amines Using O2

An efficient amidation method between readily available 1,1-dicyanoalkanes and either chiral or nonchiral amines was realized simply with molecular oxygen and a carbonate base. This oxidative protocol can be applied to both sterically and electronically challenging substrates in a highly chemoselective, practical, and rapid manner. The use of cyclopropyl and thioether substrates support the radical formation of α-peroxy malononitrile species, which can cyclize to dioxiranes that can monooxygenate malononitrile α-carbanions to afford activated acyl cyanides capable of reacting with amine nucleophiles.

One-pot multistep cascade reactions over multifunctional nanocomposites with pd nanoparticles supported on amine-modified mesoporous silica

Two kinds of multifunctional nanocomposites, SBA-15-NH2/Pd-p and SBA-15-NH2/Pd-f, with platelet-like and fiber-like morphologies, respectively, were fabricated by immobilizing Pd NPs onto amine-functionalized SBA-15. Some of the amino groups acted as anchoring sites for Pd NPs, whilst the remaining groups acted as Bronsted basic sites. As a result, the composites served as excellent multifunctional heterogeneous catalysts for one-pot multistep cascade reaction sequences. Moreover,when diffusion was the rate-determine step, SBA-15-NH2/Pd-p, with small mesopores, was superior to the fiber-like control sample, owing to its short diffusion length, a lower possibility of pore clogging, and better mass transportation for the reaction species during the catalysis.

Synthetic and mechanistic studies of metal-free transfer hydrogenations applying polarized olefins as hydrogen acceptors and amine borane adducts as hydrogen donors

Metal-free transfer hydrogenation of polarized olefins (RR′ CCEE′: R, R′ = H or organyl, E, E′ = CN or CO2Me) using amine borane adducts RR′NH-BH3 (R = R′ = H, AB; R = Me, R′ = H, MAB; R = tBu, R′ = H, tBAB; R = R′ = Me, DMAB) as hydrogen donors, were studied by means of in situ NMR spectroscopy. Deuterium kinetic isotope effects and the traced hydroboration intermediate revealed that the double H transfer process occurred regio-specifically in two steps with hydride before proton transfer characteristics. Studies on substituent effects and Hammett correlation indicated that the rate determining step of the HN transfer is in agreement with a concerted transition state. The very reactive intermediate [NH2BH2] generated from AB was trapped by addition of cyclohexene into the reaction mixture forming Cy2BNH2. The final product borazine (BHNH)3 is assumed to be formed by dehydrocoupling of [NH2BH2] or its solvent stabilized derivative [NH2BH2]-(solvent), rather than by dehydrogenation of cyclotriborazane (BH2NH 2)3 which is the trimerization product of [NH 2BH2].

Facile metal free regioselective transfer hydrogenation of polarized olefins with ammonia borane

Transfer hydrogenation of polarized olefins bearing strongly electron-withdrawing groups on one side of the double bond was achieved with ammonia borane under mild conditions without using a catalyst. Mechanistic studies proved the character of the direct H transfers proceeding stepwise with a unique hydroboration intermediate and hydride before proton transfer.

Rh-catalyzed one-pot reductive alkylation of malononitrile under transfer hydrogenation conditions

Efficient synthesis of monosubstituted malononitriles was achieved by one-pot reductive alkylation of malononitrile with carbonyl compounds via [Cp*RhCl2]2-catalyzed transfer hydrogenation reaction.

3-Butyl-1-methylimidazolinium borohydride ([bmim][BH4])-a novel reducing agent for the selective reduction of carbon-carbon double bonds in activated conjugated alkenes

A novel ionic reducing reagent, 3-butyl-1-methylimidazolium borohydride ([bmim][BH4]), was synthesized and successfully used for the selective reduction of carbon-carbon double bonds in conjugated alkenes as well as the α,β-carbon-carbon double bonds in highly activated α,β,γ,δ-unsaturated alkenes. The reagent can be regenerated and reused several times without losing its activity.

Development of pharmaceutical drugs, drug intermediates and ingredients by using direct organo-click reactions

Here we report on our studies of the use of combinations of amino acids, amines, K2CO3 or Cs2CO3 and CuSO4/Cu for catalysing green cascade reactions. We aimed to prepare the highly reactive and substituted olefin species 7 and 8, under very mild and environmentally friendly conditions, thus giving the hydrogenated products 10 and 12 through the action of Hantzsch ester (4) by self-catalysis through decreasing the HOMO-LUMO energy gaps between olefins 7/8 and Hantzsch ester (4) through biomimetic reductions. Highly useful compounds 10 to 14 were assembled from simple substrates such as aldehydes 1, ketones 2, CH acids 3, Hantzsch ester (4) and alkyl halides 5 by diversity-oriented green synthesis involving cascade olefination/hydrogenation (O/H), olefination/hydrogenation/alkylation (O/H/A) and hydrogenation/olefination/hydrogenation (H/O/H) reaction sequences in one-pot fashion with stereospecific organo- and organo-/metal-carbonate catalysis. Highly functionalized diverse compounds such as 10 to 14 are biologically active products and have found wide applications as pharmaceutical drugs, drug intermediates and drug ingredients. For the first time in organocatalysis, we report the O/H/A/TE reaction to furnish high yields of transesterification products 11 by simply mixing the reactants under proline/K2CO3 catalysis conditions. Additionally, a novel organocatalytic H/O/H reaction sequence for the synthesis of alkyl-substituted aromatics has been developed. Furthermore, for the first time we have developed organocatalysed cascade olefination/hydrogenation/hydrolysis (O/H/H) reactions to furnish highly useful materials such as 2-oxochroman-3-carboxylic acid (14kc) and 2-amino-4H-chromene-3-carbonitrile (14kj) in good yields. Experimentally simple and environmentally friendly organocatalytic two-carbon homologation through cascade O/H/H reactions of aldehydes 1, Meldrum's acid (3c), Hantzsch ester (4) and acetic acid/triethylamine in ethanol has been demonstrated. Additionally, we have developed a green synthesis of the highly substituted 1,2,3-triazole 17 from simple substrates through a two-step combination of olefination/hydrogenation/alkylation and Huisgen cycloaddition reaction sequences under stereospecific organocopper catalysis conditions. In this paper we have found strong support for our hypothesis that, "decreasing the HOMO-LUMO energy gap between olefins 7/8 and Hantzsch ester (4) will drive the biomimetic hydrogenation reaction by self-catalysis". This self-catalysis was further confirmed with many varieties of examples. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.

Environmentally friendly one-pot synthesis of α-alkylated nitriles using hydrotalcite-supported metal species as multifunctional solid catalysts

A ruthenium-grafted hydrotalcite (Ru/HT) and hydrotalcite-supported palladium nanoparticles (Pdnano/ HT) are easily prepared by treating basic layered double hydroxide, hydrotalcite (HT, Mg6Al 2(OH)16CO3) with aqueous RuCl 3·n H2O and K2[PdCl4] solutions, respectively, using surface impregnation methods. Analysis by means of X-ray diffraction, and energydispersive X-ray, electron paramagnetic resonance, and X-ray absorption fine structure spectroscopies proves that a monomeric RuIV species is grafted onto the surface of the HT. Meanwhile, after reduction of a surface-isolated PdII species, highly dispersed Pd nanoclusters with a mean diameter of about 70 A is observed on the Pdnano/HT surface by transmission electron microscopy analysis. These hydrotalcite-supported metal catalysts can effectively promote α-alkylation reactions of various nitriles with primary alcohols or carbonyl compounds through tandem reactions consisting of metal-catalyzed oxidation and reduction, and an aldol reaction promoted by the base sites of the HT. In these catalytic α-alkylations, homogeneous bases are unnecessary and the only by-product is water. Additionally, these catalyst systems are applicable to one-pot syntheses of glutaronitrile derivatives.