New Transition Metal Catalysts for Organic Reactions

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-氧配合物，Re和VV，作为各种有机转化的催化剂，包括还原、取代、加成和氧化。Re(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硅氢化反应的催化剂。这代表着这种催化剂作为氧化剂的传统作用发生了逆转。并提出了这些Re(V)-氧配合物对映体选择性合成醇和亚胺的进一步发展方向。更具体地说，将利用这些络合物独特的能力来对映体和区域选择性地减少不饱和亚胺。此外，还提出了Re-oxo催化的碳(氰化物、烯丙基、三氟甲基)和类金属(硼烷、锡烷)亲核试剂的加成反应。还提出了金属氧催化的氧化反应。例如，对钒催化的氧化动力学拆分和Re催化的对映体选择性亚硫氧化进行了研究。此外，还将开发新型Re-oxo催化的氧化转化(例如，将烯烃裂解为亚胺)。提出了一系列利用金属氧络合物的独特性质的新的转化方法。这些反应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/对映体选择性加成和串联重排/对映体选择性加成。

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.