Silyl-substituted 1,3-butadienes for Diels-Alder reaction, ene reaction and allylation reaction

Silyl-substituted 1,3-butadienes are useful building blocks and are readily applied in several types of reactions such as Diels-Alder reaction, ene reaction and allylation. They can also participate in different tandem reactions such as Diels-Alder/allylation, ene/allylation, ene/allylation/Diels-Alder reaction, ene/allylation/ene reaction and ene/allylation/Diels-Alder/allylation reaction. This feature article reviews the synthesis of silyl-substituted 1,3-butadienes, and their applications in the reaction types mentioned above, involving a tandem Diels-Alder/ene/allylation process. This article also introduces some reactions of alkenylsilanes and allylsilanes for comparison and discussion about the tandem reaction. The tandem reactions described in this article are a powerful tool to construct complicated multicyclic compounds with high selectivity and high efficiency.     

Tandem Pauson-Khand reaction and Diels-Alder reaction for access to polycycles in a one-pot reaction

Starting from easily available cyclic alkenes, enynes, and dienophiles, a tandem intermolecular Pauson-Khand reaction and Diels-Alder reaction yields polycyclic compounds in high yields.     

Iterated reaction graphs: simulating complex Maillard reaction pathways

This study investigates a new method of simulating a complex chemical system including feedback loops and parallel reactions. The practical purpose of this approach is to model the actual reactions that take place in the Maillard process, a set of food browning reactions, in sufficient detail to be able to predict the volatile composition of the Maillard products. The developed framework, called iterated reaction graphs, consists of two main elements: a soup of molecules and a reaction base of Maillard reactions. An iterative process loops through the reaction base, taking reactants from and feeding products back to the soup. This produces a reaction graph, with molecules as nodes and reactions as arcs. The iterated reaction graph is updated and validated by comparing output with the main products found by classical gas-chromatographic/mass spectrometric analysis. To ensure a realistic output and convergence to desired volatiles only, the approach contains a number of novel elements: rate kinetics are treated as reaction probabilities; only a subset of the true chemistry is modeled; and the reactions are blocked into groups.     

Modeling chlorite-iodide reaction dynamics using a chlorine dioxide-iodide reaction mechanism

The mechanism of Lengyel, Li, Kustin, and Epstein (J. Am. Chem. Soc. 1996, 118, 3708) for the oscillatory chlorine dioxide-iodide reaction accurately models the reaction in closed and open systems. We investigated whether this mechanism minus the single reaction involving chlorine dioxide models the chlorite-iodide reaction equally well. It agrees qualitatively with clock reaction results. As for open system dynamics, the mechanism predicts the existence of two steady states and bistability in very nearly the same regions where these features are found experimentally in the pH range 2-4. A discrepancy in the range of bistability emerges as pH decreases, and it cannot be remedied by taking into account chlorous acid decomposition. That we were unable to locate an oscillatory region is of greater significance. Because the chlorite-iodide reaction is sensitive to mixing effects, we incorporated a two-parameter model of imperfect mixing but still found no oscillations at physically reasonable parameter values. These discrepancies strongly suggest that to obtain predictive utility for the chlorite-iodide reaction, revision of the chlorine dioxide-iodide mechanism is required.     

Synthesis of nitro-substituted decalones by double Michael reaction,sequential Michael reaction,and by Diels-Alder reaction

4-Nitro-3-phenyl-decalones are obtained from 1-acetylcyclohexene by three different ways. Stereochemistry and reaction pathways are discussed, and, for the first time, an intermediate of a sequential Michael reaction is isolated.The Michael reaction is of great preparative value for the formation of CC bonds². We are especially interested in the stereochemistry of the double Michael reaction     

Thiourea-catalyzed Morita-Baylis-Hillman reaction

Here, we describe our studies on the thiourea-catalyzed Morita-Baylis-Hillman (MBH) reaction. Chemoselective activation of carbonyl compounds via hydrogen bonding to thiourea as a catalyst is the key to drastic rate acceleration of this reaction. The application of chiral bis-thiourea-type organocatalysts, which can form a chiral double hydrogen-bonding network, is effective for enantioselective MBH reaction. A cooperative system of bis-thiourea compounds, synthesized from 1,2-diaminocyclohexane, and a Lewis base effectively promotes the MBH reaction at lower temperature, affording the MBH adducts in 33-95% yield with 44-90% ee. A plausible transition state model of the enantioselective MBH reaction is presented.     

Intrinsic reaction coordinate calculations for reaction paths possessing branching points

A 3-21+G energy surface corresponding to the proton transfer reaction in the hydroperoxyl anion solvated by one water molecule presents interesting topological features. In particular the intrinsic reaction coordinate that begins at the transition state does not lead to a minimum but to a saddle point of second order passing through two branching points. A new strategy to obtain the true reaction path in these cases is proposed.     

The reaction force. A scalar property to characterize reaction mechanisms

The reaction force is a global property of a chemical reaction that arises when applying the Hellmann–Feynmann theorem to the potential energy surface that links reactants, products and transition states. In the present work, the reaction force is defined rigorously from the cartesian components coming out from all forces exerted over each atom of a molecular system during the chemical reaction; it is demonstrated that the reaction force is a scalar property. An erratum to this article can be found at     

The retro-Nazarov reaction

Treatment of 2-bromo-4-t-butoxy-2-cyclopentenone with an amine base in refluxing trifluoroethanol afforded a ring-opened product in moderate yield. The mechanism of the reaction has been formulated as a retro-Nazarov reaction in which an oxyallylic cation undergoes ring-opening to a dienone. Several other examples of the reaction have been established through a protocol involving the conjugate addition of an organocuprate to 2-bromo-4-t-butoxy-2-cyclopentenone followed by treatment of the adducts with base in refluxing trifluoroethanol.     

Microwave-assisted Cannizzaro reaction—Optimisation of reaction conditions

The microwave-assisted Cannizzaro reaction was studied in order to develop fully reproducible synthetic protocols for transformation of aldehydes to carboxylic acid and alcohols. Optimised were the following process parameters: power, temperature, and time. Aromatic, heteroaromatic and aliphatic aldehydes were used in the studies. It was found that furfural, thiophene-2-carbaldehyde, pyridinecarboxaldehyde and aromatic aldehydes react under mild conditions, while 1-methyl-pyrrole-2-carboxaldehyde derivatives and aliphatic aldehydes require more drastic reaction conditions and a longer exposure time to microwave radiation.     

Automatic determination of reaction mappings and reaction center information. 2. Validation on a biochemical reaction database

The correct identification of the reacting bonds and atoms is a prerequisite for the analysis of the reaction mechanism. We have recently developed a method based on the Imaginary Transition State Energy Minimization approach for automatically determining the reaction center information and the atom-atom mapping numbers. We test here the accuracy of this ITSE approach by comparing the predictions of the method against more than 1500 manually annotated reactions from BioPath, a comprehensive database of biochemical reactions. The results show high agreement between manually annotated mappings and computational predictions (98.4%), with significant discrepancies in only 24 cases out of 1542 (1.6%). This result validates both the computational prediction and the database, at the same time, as the results of the former agree with expert knowledge and the latter appears largely self-consistent, and consistent with a simple principle. In 10 of the discrepant cases, simple chemical arguments or independent literature studies support the predicted reaction center. In five reaction instances the differences in the automatically and manually annotated mappings are described in detail. Finally, in approximately 200 cases the algorithm finds alternate reaction centers, which need to be studied on a case by case basis, as the exact choice of the alternative may depend on the enzyme catalyzing the reaction.     

Recent advances on deoximation: From stoichiometric reaction to catalytic reaction

Recent advances on the deoximation reactions are reviewed in this review. It was shown that catalytic deoximation with molecular oxygen as the mild oxidant should be the developing trend of the reaction.     

Thermodynamic treatment of dibenzenechromium direct-synthesis reaction and its relation to decomposition reaction

Thermodynamic studies of the equilibrium in the direct-synthesis reaction of dibenzenechromium from benzene and chromium were carried out. The reaction of gaseous chromium with the solid ligand is shown to be the most probable mechanism of the process. The thermodynamic and kinetic stabilities of dibenzenechromium and their relation to the decomposition reaction resulting in the formation of solid chromium are discussed.     

Catalytic asymmetric Henry reaction

The classical Henry reaction, the coupling of a nitroalkane with a carbonyl compound in the presence of a base, is an important C–C bond forming reaction in organic chemistry giving β-nitroalcohols, which are useful synthons in organic synthesis. However, an asymmetric version of the reaction, that has been developed recently, gives a new dimension to the classical Henry reaction whereby the control of stereochemistry of two newly generated carbon centres has become possible. In this review, the various catalytic methods for this purpose are discussed.     

Hewitt reaction revisited

A range of alkyl phenylphosphonites are prepared from the reaction of phenylphosphinic acid with the corresponding alkyl chloroformates. A mechanism for this reaction is proposed.     

Development of an efficient and safe process for a grignard reaction via reaction caloremetry

A Grignard reaction of reactantA and phenyl magnesium chloride is used to make a pharmaceutical intermediate at the production scale. The elimination of protecting groups onA was proposed as a means to reduce synthesis costs. This new synthesis route, however, had process efficiency and safety issues associated with it: (1) build-up of unreactedA in the reactor, (2) influence ofA's particle size on the reaction rate, (3) the sensitivity of the reaction rate to the reaction temperature and to the (changing) solvent composition, and (4) the highly exothermic nature of the reaction.The Mettler RC1 Reaction Calorimeter was used to quantify the influence of solvent composition, temperature, and particle size on the reaction rate. Results indicated a dramatic effect of solvent composition and reaction temperature on the reaction rate; for example, over a temperature range of just 30°C, the reaction time decreased from more than a day to just a few minutes. At such high reaction rates, the vessel jacket could not remove the reaction heat sufficiently and the internal temperature rose adiabatically.These results were used to make process design and operation recommendations for safe and efficient plant operation with this modified Grignard reaction system.The authors would like to thank the following for their assistance in this work: E. Daugs for preparing the Grignard reagents, K.L. Gonzales for her help in running the experiments and in the subsequent data work-up; P.M. Russell for his assistance in the design of the slurry addition assembly, and K. Chritz and J. Engel for performing the HPLC analyses of the samples.     

Westphal reaction in solid-phase

[reaction: see text]. A library of cycloimonium salts has been prepared through Westphal reaction in solid-phase. By reaction of solid-support-bound azolium or azinium acetates 2, 1,2-diketones 4, and base, cycloimonium salts 5 were synthesized in good to high yield and purities.     

Visible-light-driven Cadogan reaction

Visible-light-driven photochemical Cadogan-type cyclization has been discovered. The organic D-A type photosensitizer 4CzIPN found to be an efficient mediator to transfer energy from photons to the transient intermediate that breaks the barriers of deoxygenation in Cadogan reaction and enables a mild metal-free access to carbazoles and related heterocycles. DFT calculation results indicate mildly endergonic formation of the intermediate complex of nitrobiarenes and PPh₃, which corresponds with experimental findings regarding reaction temperature. The robust synthetic capacity of the photoredox Cadogan reaction systems has been demonstrated by the viable productivity of a broad range of carbazoles and related N-heterocycles with good tolerance of various functionalities.     

The influence of dissociation reaction on ammonium nitrate thermal decomposition reaction

In order to investigate the influence of dissociation reaction on thermal decomposition of ammonium nitrate (AN), biochar was selected as an adsorbent to interfere with the dissociation of AN. The TG-DSC results showed that the notable exothermic reaction of AN with the presence of 2% or 7% biochar took place. The decomposition temperature of AN decreased with increasing amount of biochar. The notable knee point was found in the TG curves. The activation energy of AN with biochar in the initial stage was higher than that of AN itself. Remote sensing Fourier transform infrared experiments found biochar induced AN decomposition at about 190 °C, which was also confirmed by the TG-MS results. After dissociation reaction, HNO₃ (g) and NH₃ (g) were adsorbed and crystalline of AN was formed on the surface of biochar. With the increasing temperature, NH₃ escaped from the surface of biochar, while HNO₃ (g) was stayed in biochar. HNO₃ (g) catalyzed the thermal decomposition of AN and also reacted with biochar. The results indicated that dissociation reaction of AN played an important role during AN thermal decomposition process. When dissociation reaction was changed, the thermal decomposition reaction of AN would also change, catalysis or inhibition AN thermal decomposition. It is a useful reference to guide the AN additives selection and to understand the mechanism for the AN decomposition accident.

     

Impact of reaction products on the Grignard reaction with silanes and ketones

Grignard reactions with alkoxysilanes or carbonyl compounds produce alkoxymagnesium halides as by-products. Kinetic measurements for reactions of silanes and of a ketone were performed with Grignard reagents, enriched in alkoxymagnesium halides and taken in a great excess.The alkoxide-type reaction products complex tightly with Grignard reagents and enhance in this way their nucleophilicity, thus accelerating the reaction. However, alkoxides branched at α-C atom exert an unfavorable steric hindrance to reaction resulting in a decrease in the reaction rate.