Development and Study of Enzyme Functional Mimics

酶功能模拟物的开发与研究

• 批准号: 7317713
• 负责人: JAMES Patrick MORKEN
• 金额: $ 17.81万
• 依托单位: BOSTON COLLEGE
• 依托单位国家: 美国
• 财政年份: 1999
• 资助国家: 美国
• 起止时间: 1999-05-01 至 2009-06-30
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/7317713
• 关键词: boron; catalyst; chemical bond; chemical synthesis; protonation; stereochemistry; synthetic enzyme

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.

描述（由申请人提供）： 新型金属催化工艺的发展对于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。当有用的新催化工艺能够在低催化剂负载量、室温下直接在市售材料上进行时，它们可以作为全合成工作的关键，也可以作为生产基本有机结构单元的有效途径。符合这些设计标准的催化反应是拟议研究的主题。其中描述的是一个旨在引入广泛的新的和有用的催化转化的计划，这些转化是立体碳硼键的创建。核心转化是催化烯烃二硼化反应，它提供了合成上通用的邻位二硼中间体。除了开发该工艺之外，我们的目标是开发二硼加合物的合成实用性，以便可以以不对称方式从不饱和底物中获得丰富的手性官能化化合物。 具体目标是： (1)开发模块化P-N配体支架，并利用它们开发不对称诱导模型并改善反应范围。 (2) 开发基于级联序列的复杂性生成反应，涉及 C-B 键到 C-X 键的转换。 (3) 开发由前手性丙二烯的二硼化引发的合成方法。 (4)开发可有效催化硼酸乙烯酯对映选择性氢化的手性配体结构。