【作者】 朱志斌；

【导师】 施敏；

【作者基本信息】 华东理工大学 ， 应用化学， 2011， 博士

【摘要】 本论文的主要内容是对两类稳定的高张力环化合物——亚甲基环丙烷和环丙烯类化合物的反应性能研究。该两类化合物都能被酸或者金属活化,得到稳定的环丙基正离子,能发生自身开环反应和被各类试剂捕获。基于以上特性,我们发展了一系列反应方法学构建各类芳香化合物和杂环化合物。本论文分为三个部分：第一部分是基于我们小组先前研究的酸催化亚甲基环丙烷反应的拓展,这其中包括路易斯酸催化的亲核试剂对亚甲基环丙烷的开环反应,我们以1,3-环状二羰基化合物作为亲核试剂进攻活化的亚甲基环丙烷开环得到高烯丙醚化合物,该反应中,二羰基化合物经过烯醇异构,以氧原子进攻三员环(第1章,第1节)；亚甲基环丙烷在布朗斯特酸和固体酸催化下作为亲双烯体均能和亚胺发生杂Diels-Alder反应得到三员环保留的四氢喹啉类化合物(第1章,第2节)。第二部分是一类共轭体系稳定的环丙烯化合物的开环和后续的分子内和分子间的反应,该类芳基乙烯基环丙烯是由我们小组之前研究的亚乙烯基环丙烷在碱性条件下经过热重排以优秀的分离收率制备得到。根据使用的酸、金属催化剂和外加试剂的不同,发生了不同方式的环丙烯活化后的碳-碳键的断裂,引发了各类重排反应和加成反应,这其中包括布朗斯特酸催化的芳基乙烯基环丙烯和醛的加成反应制备二氢苯并[c]菲衍生物,路易斯酸催化芳基乙烯基环丙烯和缩醛加成反应制备二氢环戊并[α]衍生物,我们提出了以上反应可能经过的两种途径并通过计算化学得到验证(第2章,第1节)；铝(Ⅲ)催化芳基乙烯基环丙烯开环后作为双烯体和活化烯(炔)烃发生Diels-Alder反应和布朗斯特酸催化的芳基乙烯基环丙烯和活化烯烃发生1,4-加成反应。其中,环丙烯作为双烯体的前体而非亲双烯体在有机合成中为首例报道(第2章,第2节);金(Ⅰ)催化的芳基乙烯基环丙烯环异构化反应,该反应为首例报道的金催化的环丙烯转化(第2章,第3节)；对苯醌作为氧化剂和前亲核试剂的钯(Ⅱ)催化的芳基乙烯基环丙烯串联环异构化氧化反应(第2章,第4节)；芳基乙烯基环丙烯与当量的苯腈氯化钯制备烯丙基钯(Ⅱ)络合物以及该络合物在银(Ⅰ)和三氟甲磺酸促进的脱氢重排为苯并[c]类化合物(第2章,第5节)。第三部分是一类新型的杂原子(氮／氧原子)连接的1,6-环丙烯炔类化合物的合成,以及Grubbs一代催化剂催化的该类烯炔化合物和烯烃的串联开环／闭环分子间烯炔复分解反应。我们通过铑金属催化的[2+1]环加成反应选择性地对双炔烃进行单环丙烯化,制备了该类含有环丙烯和炔结构的化合物,并通过该化合物和另一分子的烯烃的复分解反应合成了3-吡咯啉和2,5-二氢呋喃衍生物。我们通过一系列控制实验对此首例报道的环丙烯参与的分子间烯炔复分解反应进行了机理研究,确定了启动该反应的真正活性催化剂为亚烷基钌卡宾化合物而非常见的亚甲基钌卡宾化合物(第3章)。更多还原

【Abstract】 This dissertation is carried out on the reactions of two kinds of highly strained-ring componds, which includes methylenecyclopropanes (MCPs) and arylvinylcyclopropenes (AVCPs). These componds can be activated by acids or metal catalysts to generate cyclopropane cations and then undergo ring-opening reactions or can be captured by various reagents. Enlightened by these, we developed series of methodologies for building a variety of aromatic compounds and heterocyclic compounds.The dissertation is divided into three parts:the first one is an extention based on our group’s previous studies on acid catalyzed reactions of methylenecyclopropanes, including Lewis acid catalyzed nucleophilic ring-opening of activated MCPs by oxygen atoms of the enolates derived from 1,3-diones to obtain homoallylic ethers (Chapter 1.1); Brφnsted acid and solid acid catalyzed Diels-Alder reaction of MCPs (as the dienophile) and imines to produce tetrahydroquinoline derivatives with retention of the three-membered rings (Chapter 1.2).The second part is the intramolecular/intermolecular reactions of a class of conjugate stabilized cyclopropene componds. These compounds can be easily prepared by thermal-rearrangement of vinylidenecyclopropanes (VDCPs), which have been well studied by our group before, under basic conditions in excellent isolated yields. According to the employ of varieties of acid/metal-catalysts and external reagents, different types of C-C bond cleavage of cyclopropenes took place to initiate rearrangement and addition reactions, which includes Brφnsted acid promoted addition of AVCPs with aldehydes to produce 5,6-dihydrobenzo[c]phenanthrene derivatives and Lewis acid promoted addition of AVCPs with acetals to yield dihydrocyclopenta[a]indene componds. We have proposed two reaction pathways, and verified these routes by computational chemistry (Chapter 2.1); Al(Ⅲ) catalyzed ring-opening of AVCPs and tandem Diels-Alder reactions with activated olefins which is the firstly reported appilication of cyclopropenes as pro-dienes not dienophiles, as well as Brφnsted acid catalyzed 1,4-addition reactions of AVCPs with activated olefins (Chapter 2.2); the first report Au(Ⅰ) catalyzed cycloisomerization of cyclopropenes (Chapter 2.3); Pd(Ⅱ) catalyzed tandem cycloisomerization and oxidation of AVCPs using p-benzoquinone (p-BQ) as oxidant and pro-nucleophile (Chapter 2.4); synthesis ofπ-allylpalladium complexes using AVCPs and stoichiometric amount of PdCl2(PhCN)2 and Ag(Ⅰ) and TfOH promoted further dehydrogenetive rearrangement of theπ-allylpalladium complexes to 7H-Benzo[c]fluorene derivatives (Chapter 2.5). The last part is the synthesis of a novel hetero-atom (N/O atom) tethered 1,6-cyclopropene-yne and a novel tandem ring-opening/ring-closing/cross-metathesis of 1,6-cyclopropene-ynes with olefins catalyzed by the first-generation Grubbs’ruthenium complex. The novel 1,6-cyclopropene-yne was prepared by Rhodium catalyzed mono-cyclopropenation of diynes. This synthetic protocol furnishes 3-pyrroline and 2,5-dihydrofuran derivatives straightforwardly. Several control; experiments reveal that the initiator of the reaction is alkylidenes not the common methylidene (Chapter 3).更多还原