第二部分： 碳氮偶合催化反應是有機合成上十分重要的一環，其中，關於利用銅催化將芳香滷化物以及胺類偶合的反應已經有非常多研究，但其中的反應機制尚未完全明朗，在這裡我們針對HNPh2 / iodotoluene / CuI /1,10-phenanthroline的偶合系統，介紹新找到的關於碳氮偶合反應機制的證據，以及分別利用銅一價以及銅二價催化劑進行反應，比較他們的反應性差異。 ;This article is divided into two parts： The first part： There are hundreds of billion tons of plant wastes generated every year. Scientists tried to separeate and refine to make those wastes more benefit. Lignin is one part of lignocellulose and consisted of aromatics. We expected to find out a effective way to cleave lignin into many different small molecules and then separate them very well. In order to clarify the mechanism of lignin cleavage and to find out the better conditions, many scientists using lignin model compounds in the cleavage reaction at first, especially beta-o-4 model compounds because beta-o-4 linkage is the most abundant bonds in lignin. Ketone-form beta-o-4 which the secondary alchohol functional group was oxidized can promote the cleavage of beta-o-4 bond, so starting our research on this kind model compounds, we found out many mild conditions to break them down to small molecules. We developed a new approch to break down beta-o-4 model compounds to phenol and benzoic acid with only equivalents of KOH under aerobic condition in acetonitrile at room temperature. We also found that reactions could work effectively by heating up the temperature of reaction to reflux temperature or adding Cu(II) catalyst. Finally, we proposed the mechnism of the reaction and proved by theoretical calculations. The second part： The reaction of C-N cross coupling is play a important part of organic synthesis. Among them, there had already many researches on the C-N cross coupling by copper-catalyzed between aryl halides and amines, but the reaction mechanism is not yet clear. In this article, we presented the new evidence of the mechanism of the C-N coupling reaction for the coupling system of HNPh2 / iodotoluene / CuI / 1,10-phenanthroline, and reacted with copper(I) and copper(II) catalysts respectively to compare their differences in reactivity.
