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己内酰胺铑[Rh2(cap)4]催化的杂Diels-Alder反应及C-H官能化反应研究
夏热帕提·吐孙
Subtype博士
Thesis Advisor卢崇道
2013-05-29
Degree Grantor中国科学院大学
Place of Conferral北京
Degree Discipline有机化学
Keyword己内酰胺铑rh2(Cap)4 酰基亚硝基化合物 杂diels–alder反应 炔烃 烷氧基烷基化反应
Other Abstract

己内酰胺铑 [(Dirhodium Caprolactamate) Rh2(cap)4] 是一种典型的二价酰胺铑(II)配合物。从目前的研究进展来看,Rh2(cap)4的应用主要集中在催化氧化领域上。[Rh2(cap)4/TBHP]催化体系对苄位、烯丙位、炔丙位等活化的C–H键的氧化反应、酚的氧化反应、仲胺和伯胺的氧化反应以及烯烃的氮杂环丙烷化反应等具有非常好的催化活性。该典型的酰胺铑配合物的反应性研究,对其今后的应用性扩展具有重要的借鉴意义。

本文成功开发了一种制备酰基亚硝基化合物的新方法。酰基羟胺在Rh2(cap)4催化下,以叔丁基过氧化氢(TBHP)为氧化剂,生成酰基亚硝基化合物,随之被共轭二烯原位捕捉得到杂Diels–Alder环加成产物。较之其它已知方法,该方法具有催化剂用量低(0.1 mol%)、反应条件温和、加成产物收率高等优点,同时对反应体系的适用范围进行了扩展,反应具有良好的适用性。这是使用铑配合物催化氧化此类反应的首次报道。

进一步研究了[Rh2(cap)4/TBHP]催化体系引发的端位炔烃的烷氧基烷基化反应。反应以非常好的化学选择性(苄位氧化、炔丙位氧化等几种竞争反应中优先进行炔烃的烷氧基烷基化反应)得到了中等到较高收率的2-乙烯基醚类化合物。对某些反应实例,使用该方法所得收率虽然偏低,但是仍比目前所报道的其它反应条件下的同类反应的收率高。该体系反应条件较温和,而且与卤素、胺基、羟基等官能团的兼容性也非常好。同时对反应的机理进行了研究,初步确定该反应按照自由基加成机理进行。

; Dirhodium Caprolactamate [Rh2(cap)4] is one of the famous dirhodium carboxyamidates, because of its broad applications in the catalytic oxidations and has been known as an effective catalyst for activated C–H bond oxidation such as the C–H bonds on benzylic, allylic and propargylic position; phenolic oxidation; oxidation of anilines and secondry amines, and aziridination of olefines in conjunction with tert- butyl hydroperoxide. Further studies of the catalytic characters of Rh2(cap)4 will undoubtedly extend the utility of this unique catalyst. This thesis describes an efficient developed method to generate acylnitroso compounds. Hydroxamic acids could be oxidized to acylnitroso species by tert- butyl hydroperoxide catalyzed by Rh2(cap)4 and the resulting acylnitroso compounds is trapped in situ by conjugated dienes to form hetero-Diels–Alder cycloadducts. In contrast to the reported methods, cycloadducts were obtained in high yields at catalyst loadings as low as 0.1 mol% under very mild reaction conditions. Meanwhile, the scope of the reaction was also investigated and good compatibility of substrates has been observed. The catalytic reaction reported here is the first example for the dirhodium(II)-catalyzed oxidation of hydroxamic acid derivatives. In addition, alkoxyalkylation of terminal alkynes catalyzed by efficient catalyst-oxidant[Rh2(cap)4/t-BuOOH] system was explored, by which 2-vinyl ethers were prepared in good to moderate yields with excellent chemoslectivity (alkoxyalkylation took place preferentially compare to benzylic and propargylic oxidation). Although in some cases this method gives poor yields, the yields obtained by our Rh2(cap)4-catalyzed protocol are generally still higher than other previously reported methods. Functional groups such as amine, hydroxyl group and halogens were also tolerated under this mild reaction conditions. At the same time, the mechanism for this transformation was investigated, and it is revealed that alkoxyalkylation reaction presumably occurs through direct radical addition passway. Key Words: Dirhodium Caprolactamate, Acylnitroso compounds, hetero-Diels–Alder reaction, Alkynes, Alkoxyalkylation
Document Type学位论文
Identifierhttp://ir.xjipc.cas.cn/handle/365002/2468
Collection资源化学研究室
Affiliation中国科学院新疆理化技术研究所
Recommended Citation
GB/T 7714
夏热帕提·吐孙. 己内酰胺铑[Rh2(cap)4]催化的杂Diels-Alder反应及C-H官能化反应研究[D]. 北京. 中国科学院大学,2013.
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