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

基本信息

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
项目类别：
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

项目摘要

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.

项目标题：金属催化的C-H Borylation：具有新选择的新催化剂的设计抽象的 C – H Borylation是一种合成方法，其中有机分子中的C – H键用B – H或B – B键形成B -C键。它已被广泛应用于 SP2 C – H键的功能化，但是SP和SP3 C – H键的实例已经报告。这些反应的产物是重要的中间体，它利用了 B -C键在中期下安装其他官能团的多功能性状况。在此续签应用中，我们建议提高我们对C – H的理解体现并正交开发该方法，以便可以为合成的解决方案提供解决方案生物医学界面临的问题。一些具体目标是建立在先前资金中开发的化学反应的基础上的循环，而其他具体目标是全新的。具体而言，我们建议（1）低 - 的设计定向SP2和SP3 C – H BORYLATION的配位数催化剂；（2）配体的设计元和par c – h borylations的框架；（3）C – H的碳纤维的氢化和杂环以实现正式的SP3 C – H型。我们将通过协作来追求这些目标具有无机化学和有机综合的功能的多启发式企业可以承受问题。

项目成果

期刊论文数量（25）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（6）

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
影响因子：
0
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

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
影响因子：
0
作者：
Norberg AM;Smith MR 3rd;Maleczka RE Jr
通讯作者：
Maleczka RE Jr

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

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.

Getting the sterics just right: a five-coordinate iridium trisboryl complex that reacts with C-H bonds at room temperature.