Development and Study of Enzyme Functional Mimics

描述（由申请人提供）： 新型金属催化过程的发展对立体选择性有机合成以及我们对基础有机金属化学的理解具有重要意义。当有用的新催化方法能够在低催化剂负载量下、在室温下和直接在市售材料上进行时，它们可以作为全合成努力的关键，也可以作为生产基本有机结构单元的有效途径。具有这些设计标准的催化反应是所提出的研究的主题。其中描述了一个旨在引入广泛的新的和有用的催化转化的程序，这些催化转化是立体碳-硼键的产生。中心转化是催化烯烃二硼化反应，其提供合成通用的邻位二硼中间体。除了开发这个过程中，我们的目标是开发的二硼加合物的合成效用，使丰富的阵列的手性官能化的化合物可以从不饱和底物中获得的不对称的方式。 具体目标是： (1)开发模块化的P-N配体支架，并利用它们开发不对称诱导模型和改善反应范围。 (2)开发基于级联序列的复杂性生成反应，包括C-B键到C-X键的转化。 (3)发展由前手性联烯的二硼化引发的合成方法。 (4)开发对乙烯基硼酸酯的催化对映选择性氢化有效的手性配体结构。

DESCRIPTION (provided by applicant): Development of novel metal-catalyzed processes has significant implications for stereoselective organic synthesis and also for our understanding of fundamental organometallic chemistry. When useful new catalytic processes are able to proceed at low catalyst loading, at room temperature and directly on commercially available materials, they can serve as a linchpin for total synthesis efforts and also as an efficient route to the production of basic organic building blocks. Catalytic reactions with these design criteria are the subject of the proposed research. Described within, is a program directed towards introducing a broad range of new and useful catalytic transformations which are the creation of stereogenic carbon-boron bonds. The centerpiece transformation is a catalytic alkene diboration reaction which provides a synthetically versatile vicinal diboron intermediate. In addition to developing this process, we aim to develop the synthetic utility of the diboron adducts such that a rich array of chiral functionalized compounds may be accessed from unsaturated substrates in an asymmetric fashion. Specific Aims are: (1) Develop modular P-N ligand scaffolds and employ them to develop a model for asymmetric induction and to improve reaction scope. (2) Develop complexity-generating reactions based on cascade sequences that involve conversion of C-B bonds to C-X bonds. (3) Develop synthetic methods that are initiated by diboration of prochiral allenes. (4) Develop chiral ligand structures that are effective for the catalytic enantioselective hydrogenation of vinylboronates.