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Upstream product

• 874-89-5 4-Cyanobenzyl alcohol 
• 17201-43-3 4-cyanobenzyl bromide 
• 874-86-2 4-cyanobenzyl chloride 
• 434-45-7 2,2,2-Trifluoroacetophenone 
• 105-07-7 4-cyanobenzaldehyde 
• 67-56-1 methanol 
• 1396318-76-5 bis(p-cyanobenzyl) sulfite 

Relevant academic research and scientific papers

N-Heterocyclic Carbene Catalyzed Ester Synthesis from Organic Halides through Incorporation of Oxygen Atoms from Air

Oxygenation reactions with molecular oxygen (O2) as the oxygen source provides a green and straightforward strategy for the construction of O-containing compounds. Demonstrated here is a novel N-heterocyclic carbene (NHC) catalyzed oxidative transformation of simple and readily available organic halides into valuable esters through the incorporation of O-atoms from O2. Mechanistic studies prove that the deoxy Breslow intermediate generated in situ is oxidized to a Breslow intermediate for further transformation by this oxidative protocol. This method broadens the field of NHC catalysis and promotes oxygenation reactions with O2.

Synthesis, characterization and catalytic performances of benzimidazolin-2-iminato actinide (IV) complexes in the Tishchenko reactions for symmetrical and unsymmetrical esters

A new family of benzimdazolin-2-iminato actinide?(IV) complexes [(Bim7-MeDipp/MeN)An(N(SiMe3)2)3] (An = U (3), Th (4)) and [(Bim4-MeDipp/MeN)An(N(SiMe3)2)3] (An = U (5), Th (6)) were synthesized and their solid state structures were established by single-crystal X-ray diffraction analysis. The catalytic performances of complexes 3–6 towards the homo- and cross-coupling of aldehydes (Tishchenko reaction) were studied and the thorium complexes 4 and 6 displayed moderate to high activities for the production of the corresponding symmetric and unsymmetrical esters. Coupling of aldehyde and alcohols, known as the tandem proton-transfer esterification, and the intermolecular coupling reaction between aldehyde and trifluoromethylketones were also investigated by these thorium complexes, indicating a complementary method to obtain unsymmetrical esters selectively. Plausible mechanisms for these reactions are proposed based on stoichiometric studies.

Rhodium-catalyzed synthesis of imines and esters from benzyl alcohols and nitroarenes: Change in catalyst reactivity depending on the presence or absence of the phosphine ligand

The [Rh(COD)Cl]2/xantphos/Cs2CO3 system efficiently catalyzes the reductive N-alkylation of aryl nitro compounds with alcohols by a borrowing-hydrogen strategy to afford the corresponding imine products in good to excellent yields. In the absence of xantphos, the [Rh(COD)Cl]2/Cs2CO3 catalytic system behaves as an effective catalyst for the dehydrogenative coupling of alcohols to esters, with nitrobenzene as a hydrogen acceptor. The reactivity of the rhodium catalytic system can be easily manipulated to selectively afford the imine or ester.

Thorium complexes possessing expanded ring N-heterocyclic iminato ligands: Synthesis and applications

Six and seven membered N-heterocyclic iminato ligands (L) are introduced allowing access a new class of Th(iv) complexes of the type Cp?2Th(L)(CH3). These complexes were studied in the Tishchenko reaction. Stoichiometric reactions together with kinetic and thermodynamic studies permit us to propose a plausible mechanism.

Photolytic decomposition of dibenzylic sulfites

The photolytic decay of a library of para-substituted dibenzylic sulfites has been evaluated by UV radiation in a Srinivasan-Griffin-Rayonet photochemical reactor in various deuterated solvents. The decay for each dibenzylic sulfite was examined with respect to Swain and Lupton's field constant, F. The rate of photolytic decay varies depending on the identity of the benzyl substituents. Furthermore, it has been observed that the solvent affects both the rate of sulfite photolytic decay as well as final product distribution.

Organoactinides promote the dimerization of aldehydes: Scope, kinetics, thermodynamics, and calculation studies

Surprising catalytic activities have been found for the actinide complexes Cp*2ThMe2 (1), Th(NEtMe)4 (2), and Me2SiCp″2Th(C4H9) 2(3) toward oxygenated substrates. During the catalytic dimerization of benzaldehydes to their corresponding esters, complexes 1 and 2 gave 65 and 85% yield in 48 h, respectively, while the geometry-constrained complex 3 gave 96% yield in 24 h. Exploring the effect of substituents on benzaldehyde, it has been found that, in general, electron-withdrawing groups facilitate the reaction. Kinetic study with complexes 1 and 3 reveals that the rate of the reaction is first order in catalyst and substrate, which suggests the rate equation "rate = k[catalyst]1[aldehyde]1". The activation energy of the reaction was found to be 7.16 ± 0.40 and 3.47 ± 0.40 kcal/mol for complexes 1 and 3 respectively, which clearly indicates the advantage of the geometry-constrained complex. Astonishing are the reactivity of the organoactinide complexes with oxygen-containing substrates, and especially the reactivity of complex 3, toward the dimerization of substrates like p-methoxybenzaldehyde, m/p-nitrobenzaldehyde, and furanaldehyde and the reactivity toward the polymerization of terephthalaldehyde. Density functional theory mechanistic study reveals that the catalytic cycle proceeds via an initially four-centered transition state (+6 kcal/mol), followed by the rate-determining six-centered transition state (+13.5 kcal/mol), to yield thermodynamically stable products.

Homoleptic lanthanide amides as homogeneous catalysts for alkyne hydroamination and the Tishchenko reaction

The homoleptic bis(trimethylsilyl)amides of Group 3 metals and lanthanides of the general type [Ln{N(SiMe3)2}3] (1) (Ln = Y, lanthanide) represent a new class of Tishchenko precatalysts and, to a limited extent, precatalysts for the hydroamination/cyclization of aminoalkynes. It is shown that 1 is the most active catalyst for the Tishchenko reaction. This contribution presents investigations on the scope of the reaction, substrate selectivity, lanthanide-ion size-effect, and kinetic/ mechanistic aspects of the Tishchenko reaction catalyzed by 1. The turnover frequency is increased by the use of large-center metals and electron-with-drawing substrates. The reaction rate is second order with respect to the substrate. While donor atoms, such as nitrogen, oxygen, or sulfur, on the substrate decrease the turnover frequency, 1 shows a tolerance for a large number of functional groups. For the hydroamination/cyclization of aminoalkynes, 1 is less active than the well-known metallocene catalysts. On the other hand, 1 is much more readily accessible (one-step synthesis or commercially available), than the metallocenes and might therefore be an attractive alternative catalyst.

Lanthanoid-catalysed Tishchenko reaction of mono- or di-aldehydes

Lanthanoid complexes are found to be very active catalysts for the Tishchenko reaction of aldehydes. In the presence of Cp*2LnCH(SiMe3)2 (Ln = Nd, La), esters are obtained from corresponding monoaldehydes in high yields. This method is applicable to dialdehydes. The reaction of o-phthalaldehyde proceeds intramolecularly to give phthalide quantitatively. Terephthalaldehyde and di(4-formylphenyl) ether are cleanly converted into the poly[p-(carboxymethylene)phenylene] (II) and poly[p-(carboxymethylene)(p-phenylenoxy)phenylene] (III), respectively. On the other hand, isophthalaldehyde polymerizes first and then the polymer is transformed into a macrocyclic lactone 1,5,11-trioxo-2,4;8,10;14,16-tribenzo-6,12,18-trioxacyclooctadecane (1-a) in high yields. The 18-membered macrocyclic structure of 1-a was determined by the X-ray analysis. Stoichiometric reactions of the La complex with benzaldehyde indicated the intermediacy of alkoxo complexes in the catalysis.

Oxidation of Primary and Secondary Alcohols by the Catalysis of Palladium

Saturated and unsaturated alcohols are oxidized to the corresponding ketones in good or excellent yields by using an aryl halide (phenyl bromide or mesityl bromide) as an oxidant and palladium(0) or -(II) as a catalyst (0.6-3 mol percent relative to the alcohol) in the presence of a base (NaH or K2CO3).The similar oxidation of primary alcohols provides the corresponding aldehydes and/or esters.The aldehyde/ester selectivity is correlated to the steric and electronic features of substrates.The procedure is applied to the oxidation of 1-primary,ω-primary diols to lactones.