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亚磷酸酯引发的α-酮酯(或靛红衍生物)与α,β-不饱和酮的环丙烷化反应研究
尹登
Thesis Advisor卢崇道
2017-05-29
Degree Grantor中国科学院大学
Place of Conferral北京
Degree Name硕士
Degree Discipline有机化学
Keyword环丙烷 Α-酮酯 靛红衍生物 Phospha-brook重排 α Β-不饱和酮
Abstract

环丙烷是一类有用的结构单元,存在于一些具有生物活性的天然产物和药物分子之中,该官能团也可以作为开环反应转化的前体,用于有机合成中。由于环丙烷结构固有的特点,此类结构一直吸引着有机合成工作者对这类结构合成的兴趣。本论文设计并开发了一种磷杂布鲁克(phospha-Brook)重排介导的环丙烷化反应,通过一锅连续反应实现环丙烷结构的高效构建。该连续反应通过亚磷酸二甲酯或亚磷酸二乙酯在碱性条件下去质子得到磷亲核试剂,随后对α-酮酯或靛红衍生物的酮羰基进行Pudovik加成,继而发生phospha-Brook重排,得到了α-膦酰氧基碳负离子间体;该中间体被α,β-不饱和酮捕捉,通过麦克尔加成引发的关环反应(Michael initiated ring closure reaction, MIRC)历程实现缺电双键的环丙烷化,同时磷酸酯基离去。反应产率(高至99%)和立体选择性(dr>20:1:0:0)良好至优秀。该反应生成的四取代的环丙烷化合物为1,2-顺式-1,3-反式构型,是目前其他已知合成方法难于高立体选择性合成的。从反应的净结果来看,该反应实现了α-酮酯或靛红衍生物直接对α,β-不饱和酮的环丙烷化转化。

Other Abstract

Cyclopropane is an important structural unit,presents in bioactive natural products and pharmaceuticals, and serves as synthetic precursors in transformations involving ring opening. The intrinsic features possessed by cyclopropanes have attracted continue interests from synthetic community. This thesis describes an efficient synthetic method for construction of cyclopropanes via phospha-Brook rearrangemen-mediated cascade transformations in a single pot operation.The cascade starts with deprotonation of dialkyl phosphite in the presence of base and its subsequent nucleophilic addition to the keto groups of α-ketoesters or isatin derivatives, followed by phospha-Brook rearrangemen to generate α-phosphonyloxyenolate intermediates. The intermediates are trapped by α,β-unsaturated ketones via Michael addition/ring closure to form cyclopropanes with extrusion of the phosphonyloxy group. A range of tetra-substituted cyclopropanes are prepared in high yield (up to 99%) with excellent diastereoselectivity (dr>20:1:0:0). The cyclopropane products prepared by the protocol described here adopt a 1,2-cis-1,3-trans configuration, which can hardly be obtained in a diastereoselective manner by existing cyclopanation approaches. Overall, the cascade transformations enable direct cyclopropanation of α,β-unsaturated ketones by α-ketoesters or isatin derivatives.

Document Type学位论文
Identifierhttp://ir.xjipc.cas.cn/handle/365002/4942
Collection资源化学研究室
Recommended Citation
GB/T 7714
尹登. 亚磷酸酯引发的α-酮酯(或靛红衍生物)与α,β-不饱和酮的环丙烷化反应研究[D]. 北京. 中国科学院大学,2017.
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