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: 7382502
• 负责人: F. Dean Toste
• 金额: $ 26.27万
• 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/7382502
• 关键词: Accounting; Achievement; Aerobic; Air; Alcohols; Aldehydes; Alkenes; Biological; Boranes; Carbon; Catalysis; Class; Complex; Condition; DNA Sequence Rearrangement; Development; Economics; Environmental Impact; Exclusion; Goals; Heme Iron; Imines; Iron; Ketones; Kinetics; Metals; Methods; Molybdenum; Numbers; Object Attachment; Operative Surgical Procedures; Organic Chemistry; Oxidants; Oxidases; Oxidation-Reduction; Oxygen; Peroxidase; Peroxidases; Process; Property; Reaction; Reagent; Research Personnel; Resolution; Rhenium; Role; Running; Solvents; Temperature; Transition Elements; Vanadium; allyl cyanide; base; catalyst; concept; 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络合物进行催化的广泛有用和概念新颖的策略的开发。一般来说，这些反应使用金属-氧代络合物，钒和钒，作为催化剂的各种有机转化，包括还原，取代，加成和氧化。铼（V）-二氧代配合物可用作醛、酮和亚胺的化学选择性和对映选择性硅氢化反应的催化剂。这代表了这种催化剂作为氧化剂的传统作用的逆转。提出了继续发展这些手性化合物用于醇和亚胺的对映选择性合成的建议。更具体地说，这些配合物的独特能力，对映体和区域选择性减少不饱和亚胺将被利用。此外，还提出了碳（氰化物、烯丙基、三氟甲基）和类金属（硼烷、锡烷）亲核试剂的鎓-氧代催化加成。还提出了金属-氧代催化氧化。例如，钒催化的氧化动力学拆分和钒催化的对映选择性磺氧化反应的研究。此外，还将开发新的鎓-氧代催化氧化转化（例如烯烃裂解为亚胺）。提出了利用金属-氧代配合物的独特性质开发一些新的转化。这些反应包括前所未有的金属-氧代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。