New Transition Metal Catalysts for Organic Reactions

用于有机反应的新型过渡金属催化剂

• 批准号: 7575660
• 负责人: F. Dean Toste
• 金额: $ 27.31万
• 依托单位: UNIVERSITY OF CALIFORNIA BERKELEY
• 依托单位国家: 美国
• 财政年份: 2007
• 资助国家: 美国
• 起止时间: 2007-03-12 至 2011-02-28
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/7575660
• 关键词: Accounting; Achievement; Aerobic; Air; Alcohols; Aldehydes; Alkenes; Biological; Boranes; Carbon; Catalysis; Complex; DNA Sequence Rearrangement; Development; Environmental Impact; Exclusion; Goals; Heme Iron; Imines; Iron; Ketones; Kinetics; Metals; Methods; Molybdenum; Operative Surgical Procedures; Organic Chemistry; Oxidants; Oxidases; Oxidation-Reduction; Oxygen; Peroxidases; Process; Property; Reaction; Reagent; Research Personnel; Resolution; Rhenium; Role; Running; Solvents; Temperature; Transition Elements; Vanadium; allyl cyanide; base; catalyst; economic impact; insight; metal complex; novel; novel strategies; oxidation; pressure; programs; racemization; stannane

DESCRIPTION (provided by applicant): The development of broadly useful and conceptually novel strategies for catalysis using high oxidation state transition metal complexes is proposed. In general, these reactions employ metal-oxo complexes, of rhenium and vanadium, as catalysts for a variety of organic transformations including reductions, substitution, additions and oxidations. Rhenium(V)-dioxo complexes can be employed as catalysts for chemoselective and enantioselective hydrosilylation of aldehydes, ketones and imines. This represents a reversal in the traditional role of this catalysts as oxidizing agents. The continued development of chiral versions of these rhenium(V)-oxo complexes for the enantioselective synthesis of alcohols and imines will be is proposed. More specifically, the unique ability of these complexes to enantio- and regioselectively reduce unsaturated imines will be exploited. Additionally, rhenium-oxo catalyzed addition of carbon (cyanide, allyl, trifluoromethyl) and metalloid (borane, stannane) nucleophiles is proposed. Metal-oxo catalyzed oxidations are also proposed. For example, studies on vanadium-catalyzed oxidative kinetic resolution and rhenium catalyzed enantioselective sulfoxidations are described. Additionally, novel rhenium-oxo catalyzed oxidative transformation (e.g. cleavage of olefins to imines) will be developed. Development of a number of new transformations that take advantage of the unique properties of metal-oxo complexes are proposed. Theses include unprecedented metal-oxo catalyzed de-racemization reactions, tandem oxidative cleavage/enantioselective additions and tandem rearrangements/enantioselective additions.

描述（由申请人提供）：提出了使用高氧化状态过渡金属复合物的广泛有用和概念上新颖的策略的开发。通常，这些反应采用金属氧化剂，鼻和钒的金属 - 氧气络合物，作为各种有机转化的催化剂，包括减少，取代，添加和氧化。 rhenium（v） - 二氧化物复合物可以用作醛，酮和亚胺的化学选择性和对映选择性氢硅烷化的催化剂。这代表了该催化剂作为氧化剂的传统作用的逆转。将提出这些rhenium（v） - 氧化剂复合物的手性版本的持续开发，以鉴定醇和亚胺的对映选择性合成。更具体地说，这些复合物可以利用这些复合物对映射和区域选择性降低不饱和的亚胺的独特能力。此外，提出了rhenium-oxo催化的碳（氰化物，烯丙基，三氟甲基）和金属（硼烷，stannane）核寄生虫的添加。还提出了金属氧化催化的氧化。例如，描述了有关钒催化的氧化动力学分辨率和rhenuium催化对映选择性磺胺氧化的研究。此外，将开发出新的鼻氧催化氧化转化（例如，烯烃裂解至丙氨酸）。提出了许多利用金属氧化络合物独特特性的新变换的发展。这些问题包括前所未有的金属氧化催化的去核化反应，双重氧化性裂解/对映选择性添加以及串联重排/对映选择性添加。