酰基膦作为配体或膦试剂在金属铑催化的有机反应中的应用

发布时间：2018-08-08 20:44

【摘要】：以酰基膦为缺电子膦配体,利用羰基的吸电子性质,调节磷原子上的电子云密度,促进金属铑催化醛类化合物1,2-加成反应的高效进行。酰基膦化合物不仅可以做配体,还可以作为膦试剂应用于金属铑催化的C-P键偶联反应中。本论文主要内容如下：1.有关缺电子酰基膦配体在金属铑催化加成反应中的应用研究首次将酰基膦配体应用于金属铑催化的苯硼酸对苯甲醛的1,2-加成反应中,拓展24个反应例子,其中包括芳香醛、脂肪醛和肉桂醛,最高产率可达99%。并发展(S)-BINOL为手性骨架合成缺电子酰基单膦配体。此外,还将酰基膦配体应用于其他金属铑催化的加成反应中。本课题为手性缺电子膦配体提供了新的设计方法,促进了缺电子酰基膦配体在金属催化反应中的应用,为金属催化的加成反应引入一类新的膦配体。2.有关酰基膦试剂在金属铑催化下与碘苯发生C-P键偶联反应的研究在金属铑催化C-P键偶联反应中,酰基膦试剂与碘苯发生偶联反应,合成三芳基膦类化合物,实现C-P键偶联。对酰基膦与碘苯的C-P键偶联反应进行30个例子的底物扩展,扩展了碘苯,苯甲酰基膦上苯基带有不同取代基,二芳基膦上带不同取代基的情况,其中最高产率高达98%。发展了以金属铑催化,酰基膦试剂与碘苯发生C-P键偶联反应的新方法,拓宽了酰基膦试剂的应用范围。
[Abstract]:The electron cloud density of phosphorus atom was regulated by the electron absorption property of carbonyl group with acyl phosphine as electron-deficient phosphine ligands, and the metal rhodium catalyzed 1o 2-addition reaction of aldehydes was promoted efficiently. Acyl phosphine compounds can be used not only as ligands, but also as phosphine reagents in metal rhodium catalyzed C-P bond coupling reactions. The main contents of this thesis are as follows: 1. Application of electron-deficient phosphine ligands in Rhodium catalyzed addition reaction; the first application of acyl phosphine ligands to the 1 / 2-addition reaction of metal rhodium catalyzed p-benzaldehyde with 24 examples developed, including aromatic aldehydes, The highest yield of aliphatic aldehyde and cinnamaldehyde is 99%. (S)-BINOL was used as chiral framework to synthesize electron-deficient monophosphine ligands. In addition, acyl phosphine ligands were applied to the addition reaction catalyzed by other metal rhodium. This paper provides a new design method for chiral electron-deficient phosphine ligands, promotes the application of electron-deficient phosphine ligands in metal-catalyzed reactions, and introduces a new kind of phosphine ligands .2for metal-catalyzed addition reactions. Studies on the C-P Bond Coupling reaction of Iodobenzene with Acyl phosphine Reagent catalyzed by Rhodium; in the metal rhodium catalyzed C-P bond coupling reaction, acyl phosphine reagent is coupled with iodobenzene to synthesize triarylphosphine compounds and C-P bond coupling is realized. In the C-P bond coupling reaction of acyl phosphine with iodizene, 30 examples of substrate expansion were carried out, which expanded iodobenzene, benzyl phosphine with different substituents and diaryl phosphine with different substituents, among which the highest yield was up to 98%. A new method of C-P bond coupling reaction between acyl phosphine reagent and iodobenzene catalyzed by metal rhodium has been developed and the application scope of acyl phosphine reagent has been broadened.
【学位授予单位】：北京化工大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O641.4;O621.251

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