Metal-Catalyzed C-H Borylation: Mechanism, Scope, and Applications

金属催化的 C-H 硼化反应：机制、范围和应用

• 批准号: 8109059
• 负责人: Milton Rudolph Smith
• 金额: $ 34.16万
• 依托单位: MICHIGAN STATE UNIVERSITY
• 依托单位国家: 美国
• 财政年份: 2001
• 资助国家: 美国
• 起止时间: 2001-06-01 至 2015-03-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/8109059
• 关键词: Address; Agreement; Boranes; Boron; Catalysis; Chemistry; Collaborations; Communities; Complement; Computer Simulation; Computing Methodologies; Electronics; Family; Generations; Goals; Hydrogen Bonding; Inorganic Chemistry; Iridium; Metals; Methodology; Methods; Nature; Organic Synthesis; Play; Positioning Attribute; Process; Reaction; Reagent; Reporting; Research Personnel; Role; Solutions; System; Texas; Ursidae Family; abstracting; catalyst; computer studies; design; insight; interest; professor; research study; theories

DESCRIPTION (provided by applicant): Metal-Catalyzed C-H Borylation: Mechanism, Scope, and Applications Abstract C-H borylation is a process where C-H bonds in an organic molecule react with B-H or B-B bonds forming a B-C bond. The byproducts of this process are dihydrogen from B-H reagents or a borane from B-B reagents. In most instances, this process is metal-catalyzed, and the most widely utilized systems employ iridium. The regioselectivities for C-H borylations often complement those of more commonly employed C-H functionalization methods like electrophilic aromatic substitution (EAS) or directed ortho-metalation (DoM). Although steric interactions can have a strong influence on regioselectivity, there is evidence that electronic effects may play an important, though underappreciated, role in this chemistry. Herein we propose to advance our understanding of C-H borylations and to orthogonally develop the methodology such that it can offer solutions to synthetic problems faced by the biomedical community. Specifically, we propose to (1) gain insight into the mechanistic nature of these reactions; (2) Develop new strategies for contra electronic C-H functionalizations; and (3) Invent new catalysts for atroposelective C-H functionalization. We will pursue these aims through a collaborative multi- investigator venture that bring the power of inorganic chemistry, organic synthesis, and computational methods to bear on the problem. PUBLIC HEALTH RELEVANCE: Metal-Catalyzed C-H Borylation: Mechanism, Scope, and Applications Project Narrative: New pharmaceuticals call for new chemical building blocks. Similarly, lower cost drugs will require more efficient and environmentally friendly routes to these key synthetic intermediates. Thus we looked to invent chemistry that will allow for the preparation of otherwise inaccessible molecule that may enable drug discovery, development, and production.

描述（由申请人提供）：金属催化的 C-H 硼化反应：机理、范围和应用 摘要 C-H 硼化反应是有机分子中的 C-H 键与 B-H 或 B-B 键反应形成 B-C 键的过程。该过程的副产物是来自 B-H 试剂的二氢或来自 B-B 试剂的硼烷。在大多数情况下，该过程是金属催化的，并且最广泛使用的系统使用铱。 C-H 硼基化的区域选择性通常可以补充更常用的 C-H 官能化方法，如亲电芳香取代 (EAS) 或定向邻位金属化 (DoM)。尽管空间相互作用对区域选择性有很大影响，但有证据表明电子效应可能在这种化学反应中发挥重要作用，尽管这一作用未被充分认识。在此，我们建议加深对 C-H 硼化的理解，并正交开发该方法，以便为生物医学界面临的合成问题提供解决方案。具体来说，我们建议（1）深入了解这些反应的机械性质； (2) 制定反电子C-H功能化新策略； (3)发明用于天体选择性C-H官能化的新型催化剂。我们将通过多研究者合作来实现这些目标，利用无机化学、有机合成和计算方法的力量来解决这个问题。 公共健康相关性：金属催化的 C-H 硼化：机制、范围和应用项目叙述：新药物需要新的化学结构单元。同样，成本较低的药物将需要更有效、更环保的途径来生产这些关键的合成中间体。因此，我们希望发明一种化学方法，能够制备原本无法获得的分子，从而实现药物的发现、开发和生产。