Stereoselective Atom Transfer

描述（由申请人提供）：烯烃是有机化合物的最有效入口，具有多种可控的功能。该计划的目标是发现和改进选择性烯烃氧化的各种方法，包括锇催化的氨基羟基化和二羟基化，铼催化的环氧化，溴催化的叠氮化和四氧化钌催化的氧化反应。重点放在催化氨基羟基化在两个外消旋和对映选择模式，因为这个问题提出了最大的挑战和巨大的潜在回报的合成效用。初步结果为这一领域提供了令人兴奋的机制见解。

DESCRIPTION (provided by applicant): Olefins provide a most efficient entry to organic compounds with diverse and controllable functionality. The goals of this program are to discover and improve a variety of methods for selective olefin oxidation, including osmium-catalyzed aminohydroxylation and dihydroxylation, rhenium-catalyzed epoxidation, bromine-catalyzed aziridination, and ruthenium tetroxide catalyzed oxidation reactions. Emphasis is placed on catalytic aminohydroxylation in both racemic and enantioselective modes, as this problem presents both the greatest challenges and the great potential rewards for synthetic utility. Preliminary results have provided exciting mechanistic insights in this area. Additionally, single-atom transfers mediated by osmium and other d(0)-metals, based on the exploration of the "spectator-oxo" principle, will be studied. This heretofore little explored reactivity should greatly expand the scope of the transition metal-mediated oxidation processes. The products of olefin oxidation of greatest importance as synthetic intermediates are high-energy compounds that engage in rapid and selective subsequent transformations. Chief among these are epoxides, aziridines, cyclic sulfates, and episulfonium ions. New methods for the synthesis and manipulation of these intermediates are discussed. The ultimate goal is the development and exploitation of an expanded set of highly reliable reactions for the preparation of organic compounds of use to the exciting disciplines of diversity chemistry and drug discovery.