Stereoselective Atom Transfer

描述（由申请人提供）：烯烃提供了一个最有效的入口，以有机化合物与多样化和可控的功能。该计划的目标是发现和改进各种选择性烯烃氧化的方法，包括锇催化的氨羟基化和二羟基化，铑催化的环氧化，溴催化的氮丙啶化和四氧化钌催化的氧化反应。重点放在催化氨羟基化在两个外消旋和对映选择性模式，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。初步结果提供了令人兴奋的机制在这方面的见解。 此外，还将研究基于“旁观者-氧代”原理的探索，由锇和其他d（0）-金属介导的单原子转移。这种迄今为止很少探索的反应性应大大扩展过渡金属介导的氧化过程的范围。 作为合成中间体，烯烃氧化的最重要的产物是高能化合物，它们参与快速和选择性的后续转化。其中主要的是环氧化物、氮丙啶、环状硫酸盐和episulfonium离子。这些中间体的合成和操作的新方法进行了讨论。最终目标是开发和利用一套扩展的高度可靠的反应，用于制备多样性化学和药物发现等令人兴奋的学科的有机化合物。

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.