A remarkable rate acceleration of the Baylis-Hillman reaction

Treatment of alpha-naphthyl acrylate with both aliphatic and aromatic aldehydes in the presence of DABCO (30 mol%) afforded the desired (alpha-methylene-beta-hydroxy)esters with reasonable chemical yields (51-88%) within 20 min.     

Significant rate acceleration of the aza-Michael reaction in water

The addition of amines to conjugated alkenes has been carried out in water at room temperature very efficiently without any catalyst. Significant rate acceleration of this reaction is observed in water compared to organic solvents.     

Determination of the reaction acceleration effect at an elevated hydrostatic pressure

Russian Chemical Bulletin - A method was proposed for the calculation of changes in the rate (k P /k P=0) and equilibrium constants (K P /K P=0) for chemical reactions under high hydrostatic...     

Rate acceleration of organic reaction by immediate solvent evaporation

Several types of organic reactions were accelerated by immediate evaporation of solvents because of remarkable enhancement of molecule-to-molecule contacts between reactants.     

Dramatic acceleration of the Menschutkin reaction and distortion of halide leaving-group order

Compared to structurally related linear trialkylamines, a simple macrocyclic amine with an anion-binding cavity exhibits very large rate enhancements (>10(5)) for stoichiometric N-alkylation with primary alkyl, allyl, and benzyl halides in the weakly polar solvent CDCl3. There is also a major distortion of the halide leaving-group order. For example, with benzyl halides the relative leaving-group order with a control amine is Cl (1) < Br (71) < I (160), whereas the leaving-group order with the macrocyclic amine is I (0.4) < Cl (1) < Br (8.5). Reaction with the macrocyclic amine is inhibited by the addition of DMSO, which is unusual because the Menschutkin reaction is normally enhanced by the presence of a polar aprotic solvent. Competitive inhibition studies indicate that the reaction proceeds through a prereaction complex. Effective molarities for the subsequent unimolecular N-alkylation step with 4-t-butylbenzyl halides are 4-t-BuBnCl (62,000 M) > 4-t-BuBnBr (2200 M) > 4-t-BuBnI (35 M); thus, the free energy of activation is selectively decreased for organohalides having smaller and more charge dense leaving groups. Likely reasons for this selective enhancement effect are: (a) increased transition-state stabilization due to hydrogen bonding in the macrocyclic pocket and (b) reduced entropic penalty in the transition state due to an increased fraction of prereaction complexes that are oriented in a near attack conformation. The study suggests that it should be possible to develop highly reactive macrocyclic amines that selectively sense or scavenge carcinogenic haloalkanes from the atmosphere.     

Steric acceleration of an uncatalysed ene reaction at room temperature

The bulky trityl steric buttress is used to effect an intramolecular, uncatalysed ene reaction that operates at room temperature, whilst smaller buttresses require heat.     

Association and acceleration of the thermal reaction of 5′-nitroindolinospiropyrans in solution

Conclusions Photochromic 5-nitrospiropyrans in solution form associates and complexes of the colored and colorless species, and the complex with absorption at 430 nm accelerates the thermal decolorization of the colored states. Catalysis of the thermal reaction takes place in a nonpolar and weakly polar solvent within the highly aggregated colored states.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 1987–1993, September, 1984.     

Structure-activity relationships in the acceleration of a hetero Diels-Alder reaction by metalloporphyrin hosts

At 0.33 mM in dichloromethane at 25 degrees C the cyclic metalloporphyrin hosts 5, 7, 8, and 10 accelerate 12-fold, 260-fold, 1130-fold, and 250-fold, respectively, the reaction of 1 and 2 and also bind the product 3 very strongly. These observations combined with previously measured results with hosts 6, 9, and 11 allowed us to explore the influence of host geometry changes on acceleration rates and product binding over a wide range of host molecules of different size, ranging from extremely tightly strapped to very relaxed. To estimate the Zn-Zn distance in the transition-state complex, we carried out quantum mechanical calculations (at the HF/6-31G level) for the transition state to form 3. The structure-activity relationships found for hosts 5-11, along with the structural features calculated for the transition-state structure between 1 and 2 and previously crystallographically observed for product-free hosts and for a host.product complex,(4) suggest that both host preorganization as well as host flexibility are key features leading to high acceleration rates and product binding and that it is the delicate balance between the two structural features that leads to maximum efficiency.     

Iminium ion catalysis: use of the alpha-effect in the acceleration of the Diels-Alder reaction

The alpha-effect can be used in the acceleration of the Diels-Alder reaction between a series of dienes and electron deficient dienophiles using iminium ion catalysis, providing a novel molecular scaffold capable of performing this class of catalytic process.     

Dramatic rate acceleration of the Baylis-Hillman reaction in homogeneous medium in the presence of water

[reaction: see text] In homogeneous H(2)O/solvent medium, the reaction rate of aromatic aldehydes and acrylonitrile or acrylate was greatly accelerated, which led to shorter reaction time, lower reaction temperature, and higher yield. In this reaction, Me(3)N, DMAP, DABCO, and urotropine were good catalysts. Except for low-carbon alcohols, tetrahydrofuran, 1,4-dioxane, and acetonitrile could be chosen as the solvent. Under this condition, the diastereoselective reaction of nitrobenzaldehyde and L-menthyl acrylate was realized with 88-99% de.     

Defect-induced acceleration of a solid-state chemical reaction in zinc alkoxide single crystals

A family of dinuclear (salicylaldimato)zinc(micro(2)-alkoxide) complexes show unusual behavior, decomposing to olefins and the corresponding micro(2)-hydroxide complexes under very mild conditions in the solid state. The reaction in homogeneous solution is, on the other hand, not observable, even at elevated temperatures over extended periods of time. The reaction in the solid state occurs preferentially on one crystallographic face and displays kinetics characteristic of polymorphic transformations in single crystals.     

High acceleration of the direct aldol reaction cocatalyzed by BINAM-prolinamides and benzoic acid in aqueous media

The enantioselective direct aldol reaction, organocatalyzed by recoverable BINAM-prolinamide derivatives can be highly accelerated by a catalytic amount of a carboxylic acid without a detrimental of the obtained enantioselectivities. From the study of suitable acids and reaction conditions, benzoic acid in aqueous DMF or in water was shown to give the best results with high yields and enantioselectivities. Thus, the reaction between p-nitrobenzaldehyde and acetone catalyzed by (S_a)-BINAM-l-Pro and benzoic acid can be carried out at −20 °C in only 8.5 h to give the expected product with 86% ee. In the case of butan-2-one, the iso- and the anti-isomers are obtained in a 1:1 isomer ratio up to 99% ee. Cyclohexanone gives the anti-aldol in up to 99% dr and 97% ee in only 2 h. The opposite diastereoselectivity is obtained in the case of cyclopentanone with lower ee up to 65% for the syn and 85% for the anti-isomer.     

Remarkable rate acceleration of imidazole-promoted Baylis-Hillman reaction involving cyclic enones in basic water solution

The Baylis-Hillman reaction of cyclic enones was greatly accelerated in basic water solution with imidazoles as catalysts, which resulted in short reaction time, high yields, and expanding substrate scopes. Bicarbonate solution was shown to be the optimal reaction medium for the reaction in this study. The apparent "enhanced basicity" of imidazoles accounted for the rate increase in alkaline solution.     

Heterogeneous synergistic catalysis by a palladium complex and an amine on a silica surface for acceleration of the tsuji-trost reaction

The cooperative surface-catalysis strategy of a Br?nsted acid and an organic base can be extended to a metal complex and organic base pair. A silica-supported diaminopalladium complex and a tertiary amine were prepared and characterized. The Pd-catalyzed Tsuji-Trost reaction was enhanced significantly by the presence of the tertiary amine on the same silica surface as the Pd complex.     

Uppsalator's acceleration

Semiquantitative prediction of the Uppsalator (electroosmotical oscillator developed in Uppsala) under constant voltage is confirmed via numerical solution of exact nonlinear integro-differential equations in partial derivatives (PDE). Critical voltage and characteristic features of pressure and liquid flow velocity as functions of time are reproduced with high precision. In particular, the number of inflection points per period of oscillating velocity increases with growing voltage from two to six. A new feature is demonstrated. For sufficiently high voltages the Uppsalator shows normal deceleration, i.e., the oscillation period grows with voltage. However, in some supercritical range of voltages, acceleration is observed, as expressed by decrease of the oscillation period with growing voltage. Thus, the Uppsalator at constant voltage considered earlier as an impossible phenomenon represents a great challenge for experimental verification.     

The acceleration of the hydrogen evolution reaction from acid solutions by sulfur compounds: Part II. Indium amalgam electrodes

Thiourea and its N-substituted derivatives accelerate the hydrogen evolution reaction at mercury, indium and indium amalgam electrodes. The differences in the effects observed with mercury and with indium amalgam electrodes can be accounted for in terms of differences in the adsorption of the organic compounds at the metal-solution interfaces.     

Total synthesis of the fungal metabolite (±)-acremine G: acceleration of a biomimetic Diels-Alder reaction on silica gel

A total synthesis of the bioactive tetracyclic natural product acremine G has been achieved in which a regio- and stereoselective biomimetic Diels-Alder reaction between two readily assembled building blocks, accelerated on a solid support (silica gel), forms the key step.