Metal-Catalyzed C-H Borylation: Design of New Catalysts with New Selectivities

金属催化的 C-H 硼化：具有新选择性的新型催化剂的设计

• 批准号: 10197387
• 负责人: Milton Rudolph Smith
• 金额: $ 10.42万
• 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 2020-07-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/10197387
• 关键词: Chemicals; Chemistry; Communities; Development; Drug Costs; Funding; Hydrogen Bonding; Hydrogenation; Inorganic Chemistry; Ligands; Metals; Methodology; Organic Synthesis; Pharmacologic Substance; Preparation; Production; Reaction; Reporting; Research Personnel; Route; catalyst; design; drug discovery; functional group

Project Title: Metal-Catalyzed C-H Borylation: Design of New Catalysts with New Selectivities Abstract C–H borylation is a synthetic methodology where C–H bonds in an organic molecule react with B–H or B–B bonds forming a B–C bond. It has been widely applied in the functionalization of sp2 C–H bonds, but examples of sp and sp3 C–H bonds have been reported. The products of these reactions are important intermediates, which leverage the remarkable versatility of B–C bonds for installation of other functional groups under mild conditions. In this renewal application, 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. Some of the specific aims build on chemistry that was developed in the previous funding cycle, while other specific aims are entirely new. Specifically, we propose to (1) the design of low- coordination number catalysts for directed sp2 and sp3 C–H borylation; (2) The design of ligand frameworks for meta and para C–H borylations; and (3) Hydrogenation of C–H borylated arenes and heterocycles to achieve formal sp3 C–H borylation. We will pursue these aims through a collaborative multi-investigator venture that bring the power of inorganic chemistry and organic synthesis to bear on the problem.

项目名称：金属催化C-H硼化：具有新选择性的新型催化剂设计 摘要 C-H硼基化是一种有机分子中的C-H键反应的合成方法 其中B-H或B-B键形成B-C键。它已广泛应用于 sp2 C-H键的官能化，但sp和sp3 C-H键的实例已经被发现。 报道这些反应的产物是重要的中间体，其利用了 B-C键在温和条件下用于安装其他官能团的显着多功能性 条件在这次更新申请中，我们提出要推进我们对C-H的理解 并正交发展的方法，使它可以提供解决方案，合成 生物医学界面临的问题。 一些具体的目标建立在以前资助中开发的化学基础上 这是一个新的周期，而其他具体目标则是全新的。具体来说，我们建议（1）低- （2）配体的设计 用于间位和对位C-H硼基化的骨架;和（3）C-H硼基化芳烃的氢化， 杂环以实现正式的sp3 C-H硼化。我们将通过一个合作伙伴关系来实现这些目标。 多研究者的冒险，使无机化学和有机合成的力量承担 问题所在

项目成果

Boc groups as protectors and directors for Ir-catalyzed C-H borylation of heterocycles.

• DOI: 10.1021/jo901822b
• 发表时间: 2009-12-04
• 期刊: The Journal of organic chemistry
• 作者: Kallepalli VA;Shi F;Paul S;Onyeozili EN;Maleczka RE Jr;Smith MR 3rd
• 通讯作者: Smith MR 3rd

Ir-Catalyzed ortho-Borylation of Phenols Directed by Substrate-Ligand Electrostatic Interactions: A Combined Experimental/in Silico Strategy for Optimizing Weak Interactions.

• DOI: 10.1021/jacs.7b02232
• 发表时间: 2017-06-14
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Chattopadhyay B;Dannatt JE;Andujar-De Sanctis IL;Gore KA;Maleczka RE Jr;Singleton DA;Smith MR 3rd
• 通讯作者: Smith MR 3rd

Bismuth Acetate as a Catalyst for the Sequential Protodeboronation of Di- and Triborylated Indoles.

乙酸苯二酸酯作为Di-and di-di-di-triboryed吲哚的顺序凹孔的催化剂。

• DOI: 10.1021/acs.orglett.6b00356
• 发表时间: 2016-04-01
• 期刊: ORGANIC LETTERS
• 影响因子: 5.2
• 作者: Shen, Fangyi;Tyagarajan, Sriram;Perera, Damith;Krska, Shane W.;Maligres, Peter E.;Smith, Milton R., III;Maleczka, Robert E., Jr.
• 通讯作者: Maleczka, Robert E., Jr.

Practical One-Pot C-H Activation/Borylation/Oxidation: Preparation of 3-Bromo-5-methylphenol on a Multigram Scale.

• DOI: 10.1055/s-0030-1258443
• 发表时间: 2011-03
• 期刊: Synthesis
• 作者: Norberg AM;Smith MR 3rd;Maleczka RE Jr
• 通讯作者: Maleczka RE Jr

Achieving High Ortho Selectivity in Aniline C-H Borylations by Modifying Boron Substituents.

• DOI: 10.1021/acscatal.8b00641
• 发表时间: 2018-07-06
• 期刊: ACS catalysis
• 影响因子: 12.9
• 作者: Smith MR 3rd;Bisht R;Haldar C;Pandey G;Dannatt JE;Ghaffari B;Maleczka RE Jr;Chattopadhyay B
• 通讯作者: Chattopadhyay B