New Transition Metal Catalysed Methods for Alkyl C-N Bond Formation

过渡金属催化烷基 C-N 键形成的新方法

• 批准号: EP/J007455/1
• 负责人: John Bower
• 金额: $ 10.97万
• 依托单位: University of Bristol
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2011
• 资助国家: 英国
• 起止时间: 2011 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FJ007455%2F1
• 关键词: New; Transition; Metal; Catalysed; Methods

Forming bonds between carbon and nitrogen (C-N bonds) is an important process in organic chemistry but in many instances this represents a very difficult task. The goal of this research proposal is to provide new methods, which involve metal catalysts, for particularly challenging types of C-N bond formation: Part 1. The first area will look at is forming C-N bonds in an intramolecular fashion. We will investigate cases where the carbon atom is bonded to three other atoms, of which at least one is another carbon atom. Here, we will develop a method which forms this type of C-N bond from a simple alkene precursor. In this area we will also look at the possibility of controlling which mirror image of the C-N bond we form. This particular aspect is of relevance in cases where the carbon atom of the C-N bond is attached to three other different groups.Part 2. The second area we will look at is forming C-N bonds in an intermolecular manner. These processes will be much more challenging to develop and we will use the knowledge we gain from Part 1 to aid this aspect.To facilitate these new methods we will examine the chemistry of a specific nitrogenous organic functionality that allows redox neutral C-N bond forming processes; this, in combination with a metal catalyst, will act as the source of nitrogen. The new C-N bond forming reactions will initially be developed in systems where this functionality is part of the same molecule as the alkene with which it reacts. When the new C-N bond forms a ring structure will therefore be generated. As our understanding of the reactions improves, we will see if the organic functionality and alkene can be part of different molecules. This type of C-N bond formation is anticipated to be much more challenging. This research area has been chosen because C-N bonds are vital components in living structures (e.g. amino acids) and drug compounds. By developing these new reactions we will be providing methods which allow chemists to make biologically important molecules in a quicker and more efficient manner. Indeed, these new reactions may even allow people to make molecules which are presently inaccessible. In the long term, this research can benefit wider society by enabling the development of drugs for the treatment of illnesses or by providing molecular probes for understanding biological processes. Additionally, there is an inherent need for new C-N bond forming processes as many current methods are subject to patent protection (e.g. the Buchwald-Hartwig amination) which can limit their deployment in industrial settings.Aspects of this research programme have previously been submitted as part of a successful EPSRC CAF application which was not taken up by the PI as a Royal Society URF was accepted instead.

在碳和氮之间形成键（C-N键）是有机化学中的一个重要过程，但在许多情况下，这是一项非常困难的任务。这项研究提案的目标是提供新的方法，其中涉及金属催化剂，特别是具有挑战性的类型的C-N键形成：第1部分。第一个领域将着眼于以分子内的方式形成C-N键。我们将研究碳原子与其他三个原子键合的情况，其中至少一个是另一个碳原子。在这里，我们将开发一种从简单的烯烃前体形成这种类型的C-N键的方法。在这一领域，我们还将研究控制我们形成的C-N键的镜像的可能性。这个特殊的方面在C-N键的碳原子连接到三个其他不同基团的情况下是相关的。我们要研究的第二个领域是以分子间的方式形成C-N键。这些过程的开发将更具挑战性，我们将使用我们从第1部分中获得的知识来帮助这方面。为了促进这些新方法，我们将研究特定含氮有机官能团的化学，该官能团允许氧化还原中性C-N键形成过程;这与金属催化剂结合，将作为氮源。新的C-N键形成反应最初将在这样的系统中开发，其中该官能团是与其反应的烯烃相同的分子的一部分。当新的C-N键形成时，因此将产生环结构。随着我们对反应的理解的提高，我们将看到有机官能团和烯烃是否可以是不同分子的一部分。预计这种类型的C-N键形成更具挑战性。之所以选择这一研究领域，是因为C-N键是生命结构（例如氨基酸）和药物化合物的重要组成部分。通过开发这些新的反应，我们将提供方法，使化学家能够以更快，更有效的方式制造生物重要分子。事实上，这些新的反应甚至可能使人们能够制造目前无法获得的分子。从长远来看，这项研究可以通过开发治疗疾病的药物或提供了解生物过程的分子探针来造福更广泛的社会。此外，由于许多现有方法受到专利保护（例如Buchwald-Hartwig胺化），这可能限制其在工业环境中的部署，因此对新的C-N键形成过程存在固有需求。该研究计划的各个方面先前已作为成功的EPSRC CAF申请的一部分提交，该申请未被PI接受，而是接受了皇家学会URF。

项目成果

Enantioselective Narasaka-Heck cyclizations: synthesis of tetrasubstituted nitrogen-bearing stereocenters.

• DOI: 10.1039/c6sc04466b
• 发表时间: 2017-03-01
• 期刊: Chemical science
• 影响因子: 8.4
• 作者: Race NJ;Faulkner A;Fumagalli G;Yamauchi T;Scott JS;Rydén-Landergren M;Sparkes HA;Bower JF
• 通讯作者: Bower JF

Temperature-dependent Mollow triplet spectra from a single quantum dot: Rabi frequency renormalisation and sideband linewidth insensitivity

来自单个量子点的温度相关莫洛三重态光谱：拉比频率重整化和边带线宽不敏感性

• DOI: 10.48550/arxiv.1312.4577
• 发表时间: 2013
• 作者: Wei Y

Recent developments in the use of aza-Heck cyclizations for the synthesis of chiral N-heterocycles.

• DOI: 10.1039/c7sc01480e
• 发表时间: 2017-08-01
• 期刊: Chemical science
• 影响因子: 8.4
• 作者: Race NJ;Hazelden IR;Faulkner A;Bower JF
• 通讯作者: Bower JF

Copper catalyzed Heck-like cyclizations of oxime esters

• DOI: 10.1039/c4sc00652f
• 发表时间: 2014-01-01
• 期刊: CHEMICAL SCIENCE
• 影响因子: 8.4
• 作者: Faulkner, Adele;Race, Nicholas J.;Bower, John F.
• 通讯作者: Bower, John F.