双齿亚磷酸酯配体的合成及其在铁催化的烯丙基醇取代反应中的应用

发布时间：2019-03-06 12:08

【摘要】：过渡金属催化烯丙基取代反应已经成为构建C-C键、C-N键、C-O键、C-S键以及C-P键等多种化学键的有效手段。通常制备烯丙基取代产物及其衍生物都是通过烯丙基化合物与各种亲核试剂的取代反应来获得。这些经典的合成方法一般需要已经活化了的烯丙基化合物,例如烯丙基卤代物、烯丙基酯、烯丙基碳酸酯、磷酸酯以及相关的衍生物等,这些已活化的烯丙基底物都是从相应的烯丙基醇制备得来。反应步骤繁琐,原子经济性差。因此,直接催化烯丙基醇的亲核取代反应,更具有研究意义和挑战性。而以廉价金属铁催化剂与双齿亚磷酸酯配体络合来催化烯丙基醇的取代反应鲜少有报道。本文在研究过渡金属催化烯丙基醇的取代反应时,发现Fe(OTf)2与双齿亚磷酸酯配体一起作用,能够很好的催化烯丙基醇取代反应,并取得中等到优秀的收率,在有机合成方法学上具有一定的创新性和研究意义。本课题组首先合成了六种双齿亚磷酸酯配体L1-L6,以采用3,3',5,5'-四叔丁基-2,2'-二羟基联苯为原料,“一锅法”高效合成了该类型的配体。接下来我们又考察了双齿亚磷酸酯配体在烯丙基醇取代反应中的应用,以肉桂醇与苯胺的反应为模板,考察了不同催化剂、溶剂、配体、温度、催化剂的用量对烯丙基取代反应的影响,并确定了优化后的反应条件为:在氮气保护下,5mol%Fe(OTf)2为催化剂,5mol%L4作为配体,甲苯作为溶剂,回流的条件下,反应12 h。在优化后的条件下,对芳香胺、脂肪胺、硫酚类化合物以及不同烯丙基醇类化合物进行了拓展,取得了高选择性和中等至优秀的收率。
[Abstract]:The catalytic allyl substitution reaction of the transition metal has become an effective means to construct the C-C bond, the C-N bond, the C-O bond, the C-S bond, and the C-P bond. In general, the preparation of allyl-substituted products and their derivatives is obtained by the substitution reaction of allyl compounds with various nucleophiles. These classical synthesis methods generally require the already activated allyl compounds, such as allyl halides, allyl esters, allyl carbonates, phosphate esters, and related derivatives, and the like, all of which are derived from the corresponding allyl alcohol. The reaction steps are complex and the atomic economy is poor. Therefore, the nucleophilic substitution reaction of the allyl alcohol is directly catalyzed, and the research significance and the challenge are more. And the substitution reaction of the allyl alcohol is catalyzed by the complex of the cheap metal iron catalyst and the double-tooth phosphite ligand. In this paper, when the substitution reaction of the transition metal catalyzed allyl alcohol is studied, it is found that the Fe (OTf)2, together with the didentate phosphite ligand, can be used as a good catalytic allyl alcohol to replace the reaction, and the yield of the medium to the excellent is obtained, and the method has certain innovation and research significance in the organic synthesis method. In this research group, six didentate phosphite ligands L1-L6 were synthesized, and the ligands of this type were synthesized by the "one-pot method" of 3,3 ',5,5'-tetrat-butyl-2,2 '-dihydroxybiphenyl. The application of didentate phosphite ligand in the substitution reaction of allyl alcohol was also investigated. The reaction of cinnamyl alcohol and aniline was used as the template, and the effect of different catalyst, solvent, ligand, temperature and catalyst on the reaction of allyl substitution was investigated. and the optimized reaction conditions are as follows: under the protection of nitrogen,5 mol% of Fe (OTf)2 is used as a catalyst,5 mol% of L4 is used as a ligand, and the toluene is used as a solvent, and the toluene is used as a solvent, and the reaction is carried out for 12 hours under the condition of reflux, The sulfur compounds and the different allyl alcohol compounds are expanded to obtain high selectivity and moderate to excellent yield.
【学位授予单位】：郑州大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4;O621.251

【相似文献】