Development of novel photochemical processes for C-N bond formation

氮化分子广泛应用于药物和农用化学品等高价值材料中。这些分子的很大一部分包含一个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一部分。这里将开发的化学旨在开发一个合成平台，使烷基羧酸衍生物与氮亲电试剂的一般和有效的偶联。的方法。我们将尝试开发一种镍催化的方法，用于活性羧酸与活性氮衍生物的偶联。我们将需要通过羧酸单元与羟基邻苯二胺试剂的缩合制备活性酸，并制备羟胺衍生物作为氮偶联伙伴。有了这些材料，我们将研究镍将活性酸还原成相应的烷基自由基，同时通过氧化加成顺序激活羟胺的工艺。这将使一种新型的碳氮键通过自由基-有机金属途径形成。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/可见吸收光谱。新颖的物理科学内容。该项目将提供一种新的方法来加速使用不寻常的建筑模块的高价值材料的建造。所使用的新方法和将进行的机理研究将为催化、合成化学、自由基化学和交叉偶联等领域提供额外的理解。

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.