ChemInform Abstract: Preparation of TADOOH, a Hydroperoxide from TADDOL, and Use in Highly Enantioface‐ and Enantiomer‐Differentiating Oxidations.

Abstract

diastereoselective syntheses, enantioselective syntheses diastereoselective syntheses, enantioselective syntheses (incl. cis/trans-isomerism) O 0031 -035Preparation of TADOOH, a Hydroperoxide from TADDOL, and Use in Highly Enantioface-and Enantiomer-Differentiating Oxidations.-Chlorination of TADDOL, followed by reaction with urea-hydrogen peroxide complex, generates the title hydroperoxide TADOOH, a powerful reagent for asymmetric oxidation reactions. TADOOH is successfully applied in the base-catalyzed asymmetric epoxidation of enones (I) and (III), in the chemoand stereoselective oxidation of sulfide (V) to the sulfoxide (VI) and in the Baeyer-Villiger oxidation of cyclic ketones (VII) to lactones. All three types of oxidation proceed with moderate to excellent enantioselectivities (up to 99% e.e.). The mode of stereoinduction is studied using mechanistic models for each reaction. -(AOKI, MASAO; SEEBACH, DIETER; Helv. Chim. Acta 84 (2001) 1, 187-207; Lab. Org. Chem., ETH, CH-8092 Zuerich, Switz.; EN)