非金属参与的sp~3C-H键活化构筑4-烷基-2-环戊烯-1-醇核心骨架及其在天然产物合成中的应用

发布时间：2018-06-04 17:29

本文选题：γ-位的sp3C-H活化 + yang环化反应　；参考：《兰州大学》2017年硕士论文

【摘要】：本论文由两个部分组成,第一部分综述了近年来运用C-H活化反应构筑C-C键的发展和其在合成中的应用。C-C键的构筑一直是有机化学的热点,通过C-H活化的方式来直接构筑C-C键有着步骤简便,原子利用率高的优点。该部分分别从过渡金属催化的C-H活化反应和非过渡金属催化的C-H活化两部分来介绍。金属卡宾催化的C-H活化部分主要讲述了重氮化合物及金属卡宾类化合物的经典X-H插入反应(包括C-H键,O-H键,N-H键,S-H键等)。非金属催化的C-H活化则是从不同的引发方式来介绍。第二部分则是本文的核心部分。我们在一次意外的实验中发现了一种不用过渡金属催化,通过苯并二氢吡喃-4-酮的γ-位的sp3C-H活化建立C(sp3)-C(sp3)键构筑4-烷基-2-环戊烯-1-醇核心骨架的方法。具体的合成策略是利用非金属条件下苯并二氢吡喃-4-酮重氮化合物分子间aldol缩合串联分子内Yang环化反应,选择性地发生sp3 C-H对羰基的加成反应,一步建立两个sp3C-C键,构建两个季碳中心,一个三级醇,构筑4-烷基-2-环戊烯-1-醇核心骨架。非金属条件下的角甲基sp3 C-H活化建立C(sp3)-C(sp3)键以及非光催化Yang环化反应尚未见报道,有较高的创新性。
[Abstract]:This thesis consists of two parts. In the first part, the development of C-C bond construction using C-H activation reaction and its application in synthesis are reviewed. The construction of C-C bond has been a hot spot in organic chemistry. C-C bond construction by C-H activation has the advantages of simple steps and high atom utilization. In this part, the transition metal catalyzed C-H activation reaction and the non-transition metal catalyzed C-H activation are introduced respectively. The C-H activation catalyzed by metal carbene mainly describes the classical X-H insertion reactions of diazo compounds and metal carbenes, including C-H bond, N-H bond, S-H bond and so on. Non-metallic-catalyzed C-H activation is introduced in different initiation modes. The second part is the core part of this paper. In an accidental experiment, we found a method to construct the core skeleton of 4-alkyl-2-cyclopentene-1-ol by sp3C-H activation of 纬 -site of benzodihydropyran-4one without transition metal catalysis. The specific synthesis strategy is to make use of the intramolecular Yang cyclization of the intermolecular aldol condensation of benzodihydropyran-4-one diazo compounds under nonmetallic conditions, and selectively take place the addition reaction of sp3 C-H to the carbonyl group, and establish two sp3C-C bonds in one step. Two quaternary carbon centers, a tertiary alcohol, were constructed to form the core skeleton of 4-alkyl -2-cyclopentene-1-ol. The activation of keratomethyl sp3 C-H in nonmetallic conditions to establish Cnsp3C- Cnsp3) bond and the non-photocatalytic Yang cyclization reaction have not been reported, which is highly innovative.
【学位授予单位】：兰州大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.251

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