双亚砜—钯催化烯丙基C-H键直接官能化

发布时间：2018-05-08 18:39

本文选题：钯催化 + 双亚砜　；参考：《合肥工业大学》2016年硕士论文

【摘要】：在过去十年中,对烯烃的烯丙基C-H键直接官能团化的研究引起了化学家广泛兴趣,与传统的Trost-Tsuji反应相比,这避免了对烯烃的预官能团化,符合原子经济性和环境友好等现代合成理念。许多过渡金属已经被用于促进这类反应,但钯己被证明是最好的催化剂之一,钯催化的底物范围更广而且选择性更好。White和施章杰课题组发现双亚砜配体能够有效的促进钯催化烯丙基C-H键官能团。C-O键的形成是有机合成化学中最基本转化之一,通过催化烯丙基C-H键构建C-O键已有报道,但目前使用的亲核试剂主要是羧酸类化合物(乙酸,苯甲酸等),而与羟胺类化合物直接构建C-O键还未见报道,为了拓展亲核试剂底物范围,我们研究了双亚砜-钯催化烯丙基C-H键与羟胺类化合物的反应。本文首先对反应条件进行了探究,发现使用二叔丁基双亚砜作为配体时,得到了极好的产率(100%)这是二叔丁基双亚砜首次作为配体用于构建C-O键。得到了优化反应条件：以二氯甲烷作为溶剂,二叔丁基双亚砜作为配体,1,4-对苯醌作为氧化剂,亲核试剂选择羟胺化合物N-羟基邻苯二甲酰亚胺和N-羟基丁二酰亚胺,反应条件温和。然后我们对烯烃底物进行拓展研究,得到了一系列新的化合物,接着我们对反应机理进行了研究,提出了可能性的反应机理,最后,我们对得到的产物进行了应用研究。
[Abstract]:In the past decade, studies on the direct functional groups of allyl C-H bonds of olefins have attracted widespread interest among chemists, which have avoided prefunctional groups of olefins compared with conventional Trost-Tsuji reactions. Accord with modern synthesis idea such as atom economy and environment friendly. Many transition metals have been used to facilitate such reactions, but palladium has proved to be one of the best catalysts. Palladium catalyzed substrate with wider range and better selectivity. White and Szangjie's research group found that bissulfoxide ligands can effectively promote the formation of palladium catalyzed functional group of allyl C-H bond, which is one of the most basic transformations in organic synthesis chemistry. The synthesis of C-O bond by catalyzing allyl C-H bond has been reported, but the nucleophilic reagents used at present are mainly carboxylic acid compounds (acetic acid, benzoic acid, etc.), but the direct construction of C-O bond with hydroxyamine compounds has not been reported. In order to expand the substrate range of nucleophilic reagents, the reaction of allyl C-H bonds with hydroxyamines catalyzed by bissulfoxide and palladium was studied. In this paper, the reaction conditions were studied, and it was found that the second tert Ding Ji bissulfoxide was used as ligand to construct C-O bond for the first time. The optimum reaction conditions were obtained as follows: dichloromethane as solvent, di tert Ding Ji bissulfoxide as ligand, 4-benzoquinone as oxidant, nucleophilic reagent selecting hydroxylamine compounds N-hydroxyphthalimide and N-hydroxysuccinimide. The reaction conditions are mild. A series of new compounds were obtained. Then we studied the reaction mechanism and put forward the possible reaction mechanism. Finally, we studied the application of the obtained products.
【学位授予单位】：合肥工业大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O621.251

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