Stereoselective Atom Transfer

描述(由申请人提供)：烯烃提供了一种最有效的进入有机化合物的途径，具有多种可控的功能。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Os催化的氨羟化和双羟基化，Re催化的环氧化，溴催化的氮杂环化，以及四氧化二Ru催化的氧化反应。重点放在外消旋和对映体选择性模式下的催化氨羟化，因为这个问题既是合成用途的最大挑战，也是巨大的潜在回报。初步结果为这一领域提供了激动人心的机械论见解。 此外，还将在探索“旁观者-氧代”原理的基础上，研究由Os和其他d(0)金属介导的单原子转移。到目前为止，这种鲜为人知的反应活性应该会极大地扩大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，它们进行快速和选择性的后续转化。其中最主要的是环氧化物、氮杂环丙烷、环硫酸盐和表硫离子。讨论了这些中间体的合成和操作的新方法。最终目标是开发和利用一套扩展的高度可靠的反应，以制备用于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.