摘要/Abstract

现代有机合成中, C—H功能化反应可以用于直接构建各种生物活性骨架以及增加目标分子结构的复杂性, 是对传统合成方法的有效补充, 其中惰性C(sp³)—H功能化长期以来是该领域的难点. 目前, 碘试剂已被确定为经济和生态上无害的过渡金属替代品, 在具有挑战性的C(sp³)—H功能化反应中已经取得了卓有成效的进展. 分子碘与高价芳基碘试剂、二甲基亚砜(DMSO)、过氧化物以及氧气等组合, 能够高效地催化不同反应类型的C(sp³)—H功能化反应, 在不同氧化体系下具有不同的反应特点和机制. 另外, 近年来, 过渡金属/分子碘协同催化以及含碘电化学催化等新型碘催化体系在C(sp³)—H功能化反应中也得到了前所未有的发展. 综述了2015年至今分子碘在不同氧化体系下催化的C(sp³)—H功能化反应, 希望能进一步了解分子碘的绿色催化体系, 为深入研究C(sp³)—H功能化反应提供帮助.
关键词: 分子碘, C(sp³)—H功能化, 氧化体系, 绿色化学, 电化学
In modern organic synthesis, C—H functionalization can be used to construct various bioactive skeletons quickly and directly, and increase the complexity of the target molecular structure, which becomes an effective supplement to the traditional methods. Among them, C(sp³)—H functionalization has long been a big challenge in this field. Molecular iodine has been identified as an economically and ecologically harmless transition metal substitute, and tremendous progress has been made in the challenging C(sp³)—H functionalization reaction recently. The molecular iodine-catalyzed C(sp³)—H functionalization reactions under different oxidation systems have different reaction characteristics and mechanisms. The combination of molecular iodine and hypervalent aryl iodanes, dimethyl sulfoxide (DMSO), peroxide and oxygen can efficiently catalyze the functionalization of C(sp³)—H with different mechanisms. Recently, transition-metal/iodine co-cataly- sis and iodine-containing electrochemical catalysis have also made unprecedented progress in C(sp³)—H functionalization reaction. Herein, the progress of C(sp³)—H functionalization catalyzed by iodine under different oxidation systems from 2015 to now is summarized. The research on the green catalytic system of molecular iodine in the C(sp³)—H functionalization reaction is summarized and prospected.
Key words: molecular iodine, C(sp³)—H functionalization, oxidation system, green chemistry, electrochemistry


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