Development of novel photochemical processes for C-N bond formation

开发用于 C-N 键形成的新型光化学工艺

• 批准号: 2658338
• 金额: --
• 依托单位: University of Manchester
• 依托单位国家: 英国
• 项目类别: Studentship
• 财政年份: 2021
• 资助国家: 英国
• 起止时间: 2021 至 无数据
• 项目状态: 未结题
• 来源: https://gtr.ukri.org/projects?ref=studentship-2658338
• 关键词: Development; novel; photochemical; processes; bond

Nitrogenated molecules are widespread among high-value materials like drugs and agrochemicals. A substantial fraction of these molecules contains an N-alkyl bond, which makes the development of methods for the efficient assembly of sp3 C-N bonds integral to both academic and industrial synthesis. The chemistry that will be developed here aims at developing a synthetic platform enabling the general and efficient coupling of alkyl carboxylic acid derivatives with nitrogen electrophiles.The approach.We will attempt the development of a nickel catalyzed methodology for the coupling of activated carboxylic acids with activated nitrogen derivatives. We will need to prepare activated acids by condensation of the carboxylic acid unit with hydroxyphthalamide reagents and also prepare hydroxylamine derivatives as nitrogen coupling partners. With these materials in hand we will study the development of a process where nickel reduces the activated acid to the corresponding alkyl radical while sequentially activates the hydroxylamine by oxidative addition. This will enable a novel type of carbon-nitrogen bond formation via radical-organometallic pathway.The research project will require the utilization of an array of analytical techniques to understand and quantify the reaction outcomes and also to perform mechanistic studies. This will include NMR spectroscopy, mass spectrometry and UV/Vis absorption spectroscopy.Novel physical sciences content.This project will provide a novel approach to expediate the construction of high-value materials using unusual building blocks. The novel approach used and the mechanistic studies that will be performed will provide additional understanding in the fields of catalysis, synthetic chemistry, radical chemistry and cross-coupling in general.

含氮分子广泛存在于药物和农用化学品等高价值材料中。这些分子中的相当一部分含有N-烷基键，这使得sp3 C-N键的有效组装方法的发展成为学术和工业合成的组成部分。化学，将在这里开发的目的是开发一个合成平台，使一般和有效的偶联烷基羧酸衍生物与氮electrophiles.The的approach。我们将尝试镍催化的方法的发展，活化的羧酸与活化的氮衍生物的偶联。我们将需要通过羧酸单元与羟基邻苯二甲酰胺试剂的缩合来制备活化的酸，并且还制备羟胺衍生物作为氮偶联伴侣。有了这些材料在手，我们将研究一个过程的发展，其中镍减少了相应的烷基自由基的活化酸，同时依次激活羟胺通过氧化加成。该研究项目将需要利用一系列分析技术来理解和量化反应结果，并进行机理研究。这将包括核磁共振光谱，质谱和紫外/维斯吸收光谱。新的物理科学内容。该项目将提供一种新的方法，以加快使用不寻常的积木高价值材料的建设。所使用的新方法和将进行的机理研究将提供催化，合成化学，自由基化学和交叉偶联领域的额外理解。