邻甲亚基环己二烯酮在天然产物合成中的应用

doi:10.6023/cjoc201504031

摘要/Abstract

邻甲亚基环己二烯酮, 也被统称为ortho-Quinone methides (o-QMs), 是由Fries课题组在1907年提出的, 是一个半衰期极短、反应活性极高的有机活泼中间体. 它倾向于快速地再芳构化, 这也是它极不稳定的主要原因. 其再芳构化过程主要通过三个途径: 第一, 和亲核试剂发生Michael Addition; 第二, 和2π体系底物发生Hetero-Diels-Alder reaction; 第三, 经过氧杂-6π-电环化得到苯并吡喃结构. 在天然产物有机合成中, 邻甲亚基环己二烯酮中间体时常经过第二和第三这两种再芳构化的过程来构建核心骨架, 具有高效便捷的反应特性. 作为有机活泼中间体的新成员, 邻甲亚基环己二烯酮与卡宾、自由基、碳正离子等活性中间体类似, 在有机合成中都具有重要的作用. 在这里, 综述了2009~2014年间邻甲亚基环己二烯酮中间体在天然产物有机全合成中的重要应用.

关键词: 邻甲亚基环己二烯酮, 天然产物, 有机合成

ortho-Methylene cyclohexadienones, which are collectivelly referred to as ortho-quinone methides (o-QMs), were first suggested by Fries in 1907. o-QMs are a kind of short-lived and highly reactive versatile intermediates in organic synthesis. The unstability nature of o-QMs is due to their propensity to undergo rapid rearomatisation either by Michael addition of nucleophiles or, often more usefully, by cycloaddition with 2π partners or via oxa-6π-electrocyclisation to give benzopyrans. ortho-Quinone methides were always used in the synthesis of natural products through Michael addition and cycloaddition. As a new member of the family of inherently reactive species, ortho-quinone methides are similar with radicals, carbocations, carbenes, etc. And now using o-QMs to form skeletons of natural products has become a very useful stratergy. This review contains the major application in the synthesis of natural products during 2009 to 2014.

Key words: ortho-quinone methide, natural products, organic synthesis

引用此文

艾文英, 廖道红, 雷晓光. 邻甲亚基环己二烯酮在天然产物合成中的应用[J]. 有机化学, 2015, 35(8): 1615-1626.

Ai Wenying, Liao Daohong, Lei Xiaoguang. Applications of ortho-Quinone Methides in the Synthesis of Natural Products[J]. Chin. J. Org. Chem., 2015, 35(8): 1615-1626.

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