10.1016/S0040-4039(00)95573-4
The research focuses on the enantioselective functionalization of 2-substituted 1,3-propanediols using chiral spiroketals derived from E-menthone. The study explores two methods for the selective ring-cleavage reaction of spiroketals: one promoted by titanium tetrachloride and the other by triisobutylaluminum. Key chemicals involved in the research include E-menthone as the chiral auxiliary, triisobutylaluminum as the organoaluminum reagent, titanium tetrachloride, and various reagents for functional group transformations such as benzyl bromide, acetic anhydride, and lithium triethylborohydride. The methods were applied to the preparation of (S)-2,3-dimethylbutyl phenyl sulfide, a chiral starting material for the synthesis of brassinosteroids. The study highlights the complementary nature of the two ring-cleavage methods, with the triisobutylaluminum method allowing for the recovery of E-menthone and the preparation of chiral derivatives with benzyl or acyl groups that were not accessible by the previous titanium tetrachloride method.
10.1021/ol007047+
The research explores the synthesis and transformations of complex carbocyclic compounds derived from D-glucose. The primary purpose is to develop highly stereoselective methods for constructing functionalized eight-membered ring carbocycles, which have potential applications in various fields including pharmaceuticals and natural product synthesis. Key chemicals used in the study include cyclooctenol derivative 1, ketone 2, and nine-membered ring lactone 3, as well as reagents such as triisobutylaluminum (TIBAL), tert-butyldimethylsilyl chloride, and m-chloroperoxybenzoic acid (m-CPBA). The researchers employed various reactions, including acid-catalyzed ring closures, Baeyer-Villiger oxidations, and Luche reductions, to introduce additional functionalities and achieve specific stereochemistry. The study concludes that the cyclooctenic derivatives 2 and 3 are valuable synthons for constructing highly functionalized eight-membered ring carbocycles. Although some steps are not fully optimized, the approach complements existing methodologies for synthesizing substituted eight-membered rings. The potential usefulness of related carbocycles derived from other sugars is also under investigation.
10.1002/1521-3773(20000717)39:14<2466::AID-ANIE2466>3.0.CO;2-U
The research focuses on the synthesis of a new class of synthetic carbohydrate mimetics, specifically cyclooctanic carbaglucose, which are hydrolytically stable analogues that could potentially serve as therapeutic agents. The experiments involve the use of various reactants such as methyl β-D-glucopyranoside, triisobutylaluminum (TIBAL), and the Tebbe reagent, among others. Key steps include the Claisen rearrangement of 2-methylene-6-vinyl-tetrahydropyran, which affords cyclooctanic derivatives by insertion of a C unit, and the subsequent conversion of cyclooctanol derivatives into cyclooctanic mimetics through oxidation, treatment with the Tebbe reagent, and regioselective hydroboration. The analyses used to characterize the synthesized compounds include NMR spectroscopy to assign the boat-chair conformation and confirm the β-D-gluco configuration, as well as X-ray crystallography for structural determination. The study also discusses the biological potential of these mimetics, such as glycosidase inhibition, and their stability against in vivo hydrolysis.