Stereoselective Atom Transfer

立体选择性原子转移

• 批准号: 8005235
• 负责人: KARL BARRY SHARPLESS
• 金额: $ 16.45万
• 依托单位: SCRIPPS RESEARCH INSTITUTE, THE
• 依托单位国家: 美国
• 财政年份: 2009
• 资助国家: 美国
• 起止时间: 2009-12-31 至 2011-03-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/8005235
• 关键词: Acetylene; Alkenes; Amino Alcohols; Area; Attention; Azides; Aziridines; Biodiversity; Bromine; Chemicals; Chemistry; Development; Discipline; Epoxy Compounds; Generations; Glycols; Goals; Inorganic Sulfates; Ions; Laboratories; Ligands; Masks; Mediating; Metals; Methods; Organic Synthesis; Osmium; Preparation; Process; Property; Reaction; Reagent; Research; Rewards; Rhenium; Sister; Solvents; Transition Elements; Unspecified or Sulfate Ion Sulfates; Water; Work; base; catalyst; drug discovery; high energy compound; improved; insight; oxidation; process optimization; programs; ruthenium tetraoxide

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.

描述（由申请人提供）：烯烃为具有多样化且可控功能的有机化合物提供了最有效的途径。该项目的目标是发现和改进多种选择性烯烃氧化方法，包括锇催化的氨基羟基化和二羟基化、铼催化的环氧化、溴催化的氮丙啶化和四氧化钌催化的氧化反应。重点放在外消旋和对映选择性模式下的催化氨基羟基化，因为这个问题既带来了最大的挑战，也带来了合成应用的巨大潜在回报。初步结果为该领域提供了令人兴奋的机制见解。 此外，基于对“旁观者氧化”原理的探索，还将研究由锇和其他 d(0)-金属介导的单原子转移。这种迄今为止很少被探索的反应性应该会极大地扩展过渡金属介导的氧化过程的范围。 作为合成中间体最重要的烯烃氧化产物是参与快速和选择性后续转化的高能化合物。其中最主要的是环氧化物、氮丙啶、环状硫酸盐和环鎓离子。讨论了合成和操作这些中间体的新方法。最终目标是开发和利用一系列扩展的高度可靠的反应来制备有机化合物，这些有机化合物可用于令人兴奋的多样性化学和药物发现学科。