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: 7900111
• 负责人: F. Dean Toste
• 金额: $ 5.12万
• 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/7900111
• 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）：提出了使用高氧化态过渡金属配合物开发广泛有用且概念上新颖的催化策略。一般来说，这些反应采用铼和钒的金属氧配合物作为各种有机转化的催化剂，包括还原、取代、加成和氧化。铼(V)-二氧配合物可用作醛、酮和亚胺的化学选择性和对映选择性氢化硅烷化的催化剂。这代表了这种催化剂作为氧化剂的传统作用的逆转。建议继续开发这些铼(V)-氧配合物的手性版本，用于醇和亚胺的对映选择性合成。更具体地说，将利用这些配合物对映体和区域选择性还原不饱和亚胺的独特能力。此外，还提出了铼氧催化碳（氰化物、烯丙基、三氟甲基）和类金属（硼烷、锡烷）亲核试剂的加成。还提出了金属氧催化的氧化。例如，描述了钒催化的氧化动力学拆分和铼催化的对映选择性磺化氧化的研究。此外，还将开发新型铼氧催化氧化转化（例如烯烃裂解为亚胺）。提出了利用金属氧配合物的独特性质开发许多新的转化。这些包括前所未有的金属氧催化的去外消旋反应、串联氧化裂解/对映选择性加成和串联重排/对映选择性加成。