New Transition Metal Catalysts for Organic Reactions

描述（由申请人提供）：建议使用高氧化态过渡金属配合物开发广泛有用和概念新颖的催化策略。一般来说，这些反应使用金属-氧配合物，铼和钒，作为催化剂的各种有机转化，包括还原，取代，添加和氧化。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硅氢化反应的催化剂。这代表了催化剂作为氧化剂的传统作用的逆转。本文建议继续开发这些铼(V)-氧配合物的手性版本，用于对映选择性合成醇和亚胺。更具体地说，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将被利用。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）亲核试剂的加成反应。还提出了金属氧催化氧化。例如，钒催化的氧化动力学分解和铼催化的对映选择性亚砜化反应的研究。此外，将开发新的铼氧催化氧化转化（如烯烃裂解成亚胺）。提出了一些利用金属-氧配合物独特性质的新转化的发展。这些研究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.