自由基形式烯烃双烷基化反应研究进展

doi:10.6023/cjoc202312020

摘要/Abstract

烯烃双官能团化反应是实现烯烃衍生化并构建分子多样的重要方法,通过双烷基化反应在烯烃两个碳原子上连续构建C(sp³)—C(sp³)键是最有效的功能性烷基化合物的构建方法之一。由于烷基化试剂活性较高,烯烃烷基化反应通常伴随着区域选择性差,副反应多等问题。近十年来,随着自由基反应研究的深入发展,自由基形式的烯烃双官能团化反应取得了重要进展,而实现高选择性双烷基化反应依然存在挑战。这篇综述旨在对自由基形式的烯烃双烷基化反应进行一个详尽地总结,从分子内环化-分子间偶联反应,烯基硼盐自由基加成、1,2-烷基迁移反应,差异性烷基化试剂和烯烃三组分烷基化反应这三种不同的反应模式中阐述如何实现高区域选择性烯烃双烷基化过程。

关键词: 烯烃双烷基化, 区域选择性, 烷基自由基, 过渡金属催化, 光催化

Difunctionalization of alkenes constitutes a critical route for alkene derivatization and construction of molecular complexities. Yet dialkylation of alkenes allows the continues construction of two new C(sp³)—C(sp³) bonds which is one of the most effective ways for functional alkane synthesis. Because of the high reactivity of alkyl reagents, problems such as poor regioselectivity and side reactions always appear in alkene alkylation process. In recent ten years, with the further development in radical mediated reactions, significant progress has been seen in difunctionalization of alkenes through radical path. However, challenges still exist in the implement of high selectively dialkylation of alkenes. This review aims to give a comprehensive overview about the radical involved alkene dialkylated reaction. The regioselectivity control of this reaction is elaborated from three different reaction modes: intramolecular cyclization-intermolecular alkylation, alkyl radical addition- 1,2-migrated alkylation of alkenyl boron ate complexes and three-components reaction of alkenes with disparate alkylated reagents.

Key words: alkene diakylation, regioselectivity, alkyl radical, transition-metal catalysis, photocatalysis

引用此文

陆玲依, 邱晓东. 自由基形式烯烃双烷基化反应研究进展[J]. 有机化学, doi: 10.6023/cjoc202312020.

Lu Lingyi, Qiu Xiaodong. Recent Progress in Radical Involved Alkene Dialkylation[J]. Chinese Journal of Organic Chemistry, doi: 10.6023/cjoc202312020.

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