【作者】 潘磊；

【导师】 孙良东；

【作者基本信息】 天津大学 ， 有机化学， 2007， 硕士

【摘要】 锂卤类卡宾近年来成为了人们研究的热门,由于其结构的特殊性,它们可以和很多结构例如C=C, C-C, C-H等发生反应,并且很多时候都能发生重排,由于它们与各种化合物反应的多样性,已经使之成为重组碳骨架的重要化合物。特别是它们和环状化合物的反应,由于其在立体选择性和区域选择性的优越性,可以使它们参与的反应只生成单一的目标产物。近年来有多篇环丁酮系列化合物与重氮类卡宾反应生成环戊-2-烯酮系列化合物的报道。参考此类文献,本文首次以二碘甲烷和丁基锂生成锂碘类卡宾中间体,与环丁烯酮系列化合物进行反应,利用双键对重排时碳正离子的稳定作用,可以用一步反应直接生成单一的重排扩环产物环戊-2-烯酮系列化合物。这比近年来报道的环丁酮系列化合物扩环经两步反应生成环戊-2-烯酮系列化合物少用了一步,且反应条件温和安全,并且初步从反应物配比、溶剂等影响反应的条件进行了优化,并且初步提出了该反应可能的反应历程。更多还原

【Abstract】 Recently,Li/Hal Carbenoid have become the hot research field. As a result of their special structures, they can react with such structures as C=C, C-C, C-H and so on,with rearrangement happened sometimes. Because the diversities revealed in reaction with each kind of compounds, they become the significant compounds to reorganize carbon skeleton.Specially, they have predominant stereoselectivity and region-selectivity, result in the sole goal product when they react with cyclo- compound.In recent years, it is reported that on the reactions of cyclobutanone series compounds with diazo carbenoids to give adducts of the cyclobutenone series compounds in many literatures. Refers to this kind of literatures, this article is performed firstly by diiodomethane and n -Butyllithium, with the Li/I Carbenoid as intermediate which react with cyclobutenone series compounds, utilizing the carbon cation’s stabilization when it is rearranged due to double bonds, producing directly the sole rearranged and ring-expanding cyclopent-2-enone series compounds by one step. Compared with the reaction of the ring-enlargement of cyclobutanone series compounds to give cyclopent-2-enone by two steps which reported the recent years, it has less procedure, mild and safe reactive condition. It is initially carried on the planty of attempts on reactant allocated proportion, the solvent and so on which effect the reaction, and initially proposed the possible mechanism of reaction.更多还原