10.1021/ol802330h
The research focuses on the development of an asymmetric formal carbo [3 + 3] cycloaddition reaction using diphenylprolinol silyl ether as an organocatalyst. The reaction proceeds through a domino Michael/Knoevenagel condensation process, starting from R,?-unsaturated aldehydes and dimethyl 3-oxopentanedioate. The study investigates the influence of various reaction parameters, including the molar ratio of reagents, solvent, catalyst choice, and additives. The main reactants are cinnamaldehyde (R,?-unsaturated aldehyde) and dimethyl 3-oxopentanedioate. The reaction's success is highly dependent on the stoichiometry of the reactants, with optimal results achieved using equimolar amounts. The reaction's efficiency and enantioselectivity are influenced by the catalyst, with diphenylprolinol trimethylsilyl ether and its derivatives being tested. The addition of benzoic acid as an additive enhances the reaction yield and enantioselectivity. The analysis of the reaction products is performed using HPLC on a chiral phase to determine the enantiomeric excess (ee), and the structures of the synthesized compounds are confirmed by spectroscopic techniques such as 1H NMR, 13C NMR, and IR. The research demonstrates the synthesis of cyclohexenone derivatives with excellent enantioselectivity and further explores one-pot transformations to more complex cyclohexane derivatives, showcasing the synthetic utility of the developed method.
10.1021/jo00167a054
The research focuses on the decarboxylation of aromatic carboxylic acids catalyzed by Nafion-H, a sulfonated tetrafluoroethylene-based cation exchange resin. The purpose of the study was to investigate the efficiency of decarboxylation reactions for various polymethylbenzenecarboxylic acids and to understand the role of the p-methyl group in stabilizing the intermediate products. The conclusions drawn from the study indicate that the presence of p-methyl groups enhances the decarboxylation process, with mesitylenecarboxylic acid and pentamethylbenzoic acid being decarboxylated more efficiently than 2,3,5,6-tetramethylbenzoic acid. The study also involved the reaction of dimethyl 3-oxoglutarate with 1,3-dicarbonyl compounds, leading to the formation of various cyclic compounds, including bicyclo[3.3.1]nonanes and isophthalates.