联烯的自由基反应

摘要/Abstract

联烯是含有1,2-丙二烯官能团的重要化合物,具有很高的反应活性.概述了联烯及其衍生物的自由基反应,包括分子间自由基链加成和分子间—分子内自由基串联加成反应,及其在天然产物中的应用.联烯进行分子间自由基链加成反应时,自由基对联烯的加成既可发生在中间碳原子上,也可发生在末端碳原子上,主要取于所形成中间体的稳定性,空间效应、电负性和溶剂等因素也有影响.一般以碳为中心的自由基(如CH₃·, CCl₃· 等)易进攻末端碳原子,而以杂原子为中心的自由基(如Br·, RS·, ArSO₂·等)易进攻联烯的中心碳原子.联烯及其衍生物也易与烯烃、联烯、烯炔和乙烯酮进行[2＋2]环加成反应,还可以与卡宾环丙烷化,这些反应都是通过自由基机理进行的.

关键词: 联烯, 自由基, 加成反应, 环加成, 合成应用

Allenes, which contain the functional group of 1,2-propadiene, are highly reactive. In this paper, we review some free-radical reactions of allenes. The application in natural product synthesis is also described. Substituted allenes undergo rather facile radical chain addition reactions. Attack by a radical speciescan occur at either the central or the terminal C atom. In the case of addition, the preferred route is generally that forming the possibly more stable free-radical intermediates. The steric effect, electronegativity and solvent effect shoulde also be considered. In general, carbon-centered free radicalssuch as CH₃· and CCl₃· add mostly to the terminal carbon atom while heteroatom-based free radicals such as Br·, RS·, ArSO₂· and R₃Sn· add preferentially to the central carbon atom. Substituted allenes can undergo a varietyof [2+2] cycloaddition reactions with alkenes, allenes, enynes and ketenes and also undergo a cyclopropanation with carbenes via a biradical mechanism.

Key words: allene, radical, addition reaction, cycloaddition, synthetic application

引用此文

潘峰, 傅春玲, 麻生明. 联烯的自由基反应[J]. 有机化学, 2004, 24(10): 1168-1190.

PAN Feng, FU Chun-Ling, MA Sheng-Ming. Radical Reactions of Allenes[J]. Chinese Journal of Organic Chemistry, 2004, 24(10): 1168-1190.

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