【作者】 徐晓红；

【导师】 张前；

【作者基本信息】 东北师范大学 ， 有机化学， 2010， 硕士

【摘要】 乙烯基环丙烷化合物有高度的反应活性,在有机合成中有着重要的作用,日益受到人们的关注。乙烯基环丙烷首先形成烯丙基金属的中间体,继而发生一系列反应,主要反应有:加成反应、环加成反应、环异构化反应、复分解反应等等。3-氧杂二环[3.1.0]己烷类化合物是一些具有重要生物活性天然产物的基本结构单元,也是一些具有重要药物活性化合物的基本构架。3-氧杂二环[3.1.0]己烷衍生物的合成方法研究是有机合成化学的研究热点之一。通常,合成3-氧杂二环[3.1.0]己烷衍生物的主要方法包括:烯丙基重氮化合物的分子内环合反应、二溴环丙烷的金属卡宾插入反应、烯炔在过渡金属作用下环和、自由基环合反应、环丙烷类化合物的氧化反应、水解反应等等。但是,现有方法存在诸如原料局限性较大,所用试剂或催化剂昂贵,反应条件苛刻等问题。最近,我们研究小组基于易得的乙酰乙酰芳胺类化合物,对其亚甲基进行官能化,利用多米诺反应,一步、高效地合成了呋喃并喹啉类生物碱[1],构建了天然产物Martinelline的分子骨架[2],高产率获得了亚胺内酯,二氢化喹啉酮和内酰胺类衍生物。另外,直接从活泼亚甲基化合物和2,3-二溴丙酰胺出发,经一步多米诺反应构建3-氮杂二环[3.1.0]己烷衍生物。乙烯基环丙烷类化合物有高度的反应活性,在有机合成中有着重要的作用,日益受到人们的关注。本文从活泼亚甲基化合物出发制备乙烯基环丙烷类化合物,以创建简洁方法构建3-氧杂二环[3.1.0]己烷衍生物为目标,继而发展一种较为通用的合成环丙烷并五元环类化合物的策略。本论文拟在前期工作的基础上,从易得的乙烯基环丙烷类化合物出发,和N-溴代丁二酰亚胺(NBS)作用,经过反应条件的选择、优化,发展了一种合成3-氧二环[3.1.0]己烷衍生物的新策略。更多还原

【Abstract】 Vinyl cyclopropane compounds with a high degree of reactivity in organic synthesis plays an important role for increasing attention. First, the formation of vinyl cyclopropaneΠ-allyl-metal intermediate, followed by a series of reactions, the main reactions: addition reaction, cycloaddition reactions, ring isomerization reaction, metathesis, etcRecently, our team based on easy to get a dual activation of cyclopropane derivatives in stannic chloride-catalyzed ring-opening / re-cyclization domino reaction of highly selective, step and efficient synthesis of furan and quinoline alkaloids, to build a natural product Martinelline molecular skeleton .In our thesis we report a novel method for the synthesis of the tricyclic core of Martinellic acid.β-Hydroxymethylcyclopropanylamides have the structure characters of both cyclopropyl amides, and cyclopropyl carbinol. On treatment with an acid, cyclopropyl carbinyl cation intermediate could be formed from cyclopropyl carbinol. This carbocation will undergo either ring expansion to give a cyclobutyl cation or ring cleavage to give a homoallyl cation to relieve ring strain.In addition, the active methylene compounds and 2,3 - dibromo-propionamide to build a domino reaction of 3 - azabicyclo [3.1.0] hexane derivatives with a step. Based on departure from the active methylene compounds, prepared by functionalization of the preparatory work for the basis of cyclopropane , this paper is intended to develop simple methods to build 3 - oxa-bicyclo [3.1.0] hexane derivatives as the goal, to perfect a Cyclopropane synthesis, and five-membered ring derivatives strategy commonly.3 - oxa-bicyclo [3.1.0] hexane compounds have important biological activity of the basic structural units of natural products, but also a number of important basic framework of pharmaceutical active compounds. 3 - oxa-bicyclo [3.1.0] hexane derivatives research is one of the hot of organic synthetic chemistry research. Typically, the synthesis of 3 - oxa-bicyclo [3.1.0] hexane derivatives, the main methods include: Allyl Diazo compounds combined intramolecular reaction of dibromo-cyclopropane-metal carbene insertion reaction, enyne in the under the action of transition metal ring and the free radical cyclization reaction of cyclopropane compounds oxidation, hydrolysis and so on. However, the limitations of existing methods exist, such as higher raw material, the expensive reagents or catalysts, harsh reaction conditions and so on.This paper intends to base on the work front, from the molecular design proceeding from the easily avalible vinyl cyclopropane compounds and small organic molecules NBS, through the choice of reaction conditions to optimize the new strategy of synthetic 3 oxa-bicyclo [3.1.0] hexane derivatives.更多还原