【作者】 毕锡和；

【导师】 刘群；

【作者基本信息】 东北师范大学 ， 有机化学， 2006， 博士

【摘要】 自从1910年Kelber首次合成α-苯甲酰基二甲硫缩烯酮以来,经过近百年的发展,α-羰基二硫缩烯酮化学已经在合成有机化学中占有了重要一席,特别是近三十年来发展更快,每年都有相当数量的文章出现,并有数篇综述对这些工作进行了总结。一般来说,基于α-羰基二硫缩烯酮化学的反应主要为:与金属有机试剂的选择性加成反应,与氮亲核体的共轭加成反应,α?碳原子的亲核性及相关反应,烷硫基作为硫醇的替代试剂的应用及基于如上反应的合成应用。在众多的α-羰基二硫缩烯酮类化合物中,α-烯酰基二硫缩烯酮具有易于制备,官能团多等特点。从结构上看,α-烯酰基二硫缩烯酮属于1,5-双亲电的双Michael受体,可与亲核体(Michael给体)发生亲核加成及亲核加成消除等反应。此外,α’-位官能团及烷硫基的变化将对该类化合物的性质产生明显的影响。因此,α-烯酰基二硫缩烯酮的合成及其在合成中的应用研究是一重要的研究课题。发展新的基元反应和新的合成方法是有机化学创新进步的基础。在本课题组常年从事α-羰基二硫缩烯酮化学研究的基础上,本论文利用合成设计、以α-烯酰基二硫缩烯酮的合成为工作基础,以发展新基元合成反应和合成新方法为目标,创建了一种新的[5 + 1]成环策略,由此建立了一种通用性强、步骤简洁的合成多取代六员碳环、多取代含氮及含硫六员杂环化合物的新方法。同时,从α-烯酰基二硫缩烯酮类化合物出发,对经分子内Anti-Michael反应合成含氧,氮,硫五员杂环化合物的合成方法学进行了较为深入的探讨。论文工作主要包括以下两大部分七个方面的内容。第一部分,α-烯酰基二硫缩烯酮作为1,5-双亲电五碳合成子的[5 + 1]成环策略--构筑多取代六员碳环、含氮及含硫六员杂环化合物的新方法。包括:1.设计合成了新的α-乙酰基二硫缩烯酮化合物,然后经与各种醛的缩合反应,制备了一系列α-烯酰基二硫缩烯酮化合物。2.创建了区域专一性的[5C + 1C]成环策略。利用[5C + 1C]成环策略合成了一系列多取代酚类化合物,通过中间体的捕捉,提出了可能的环合芳构化反应机理。3.通过调控反应条件,以α-烯酰基二硫缩烯酮与硝基烷烃的[5C + 1C]成环为基础,实现了多取代环己烯酮的合成,并且发现该反应具有很高的立体选择性。4.作为[5C + 1C]成环策略的扩展,实现了α-烯酰基二硫缩烯酮与胺的[5C + 1N]更多还原

【Abstract】 Since Kelber first synthesized theα?benzoyl ketene-(S,S)-acetal in 1910,α-oxo ketene-(S,S)-acetals chemistry has become an important division in organic chemistry through the development of near one hundred years. Particular in recent three decades, quite amount of documents have been published in this area, and several reviews were successively reported to summarize these results. Generally, the reaction types involovingα-oxo ketene-(S,S)-acetals mainly include the regioselective addition-aromatization with organometallic reagents, conjugate addition-cyclization with nitrogen nucleophilic species, nucleophilic reactions ofα-carbon, acting as odorless dithiol equivalents in thioacetalization and Michael additions, as well as the synthetic applications based on the above reactions.Among the variousα-oxo ketene-(S,S)-acetals,α-alkenoyl ketene-(S,S)-acetals are easier to prepare and bear much more functionalities. From the view of structure,α-alkenoyl ketene-(S,S)-acetals contain two enone fragments, so they should have the potential to be attacked two times by binucleophilic species, which could result in the formation of six-membered ring systems. In addition, the variations of the substituents atα’-position and the alkylthio groups have the significant effect on their reactivity. Therefore, studies on the synthesis and the applications ofα-alkenoyl ketene-(S,S)-acetals should be a valuable research project.Developments of new basic reactions and new synthetic methods are the basis for the innovation and advance of organic chemistry. Based on the research achievement of our group inα-oxo ketene-(S,S)-acetal chemistry in the past fifteen years, my thesis starts from the synthesis of newα-alkenoyl ketene-(S,S)-acetals through synthetic design, aming to develop new basic reactions and new synthetic methods for interesting cyclic molecules, particularly, developing a new [5 + 1] synthetic strategy to provide a general and simple route to polysubstituted six-membered ring systems. At the same time, starting from theα-alkenoyl ketene-(S,S)-acetals, investigations were also carried out on the synthetic methodology for five-membered oxygen-, nitrogen- and sulfur-containing heterocycles by intramolecular anti-Michael addition. The contents in this thesis mainly includes two parts and seven aspects.In the first part, we utilizedα-alkenoyl ketene-(S,S)-acetals as the 1,5-bielectronic更多还原