自由基-极性交叉转化反应在天然产物全合成中的研究进展

doi:10.6023/cjoc202410003

摘要/Abstract

自由基-极性交叉转化(RPCO)是一类链接自由基中间体和离子型中间体的串联反应, 因此可以一步构建多根化学键, 进而快速提高分子复杂度. 近几十年来, 已有多个课题组利用RPCO为关键反应, 完成萜类、生物碱、木脂素和甾体等天然产物的全合成. 但目前, 与此类反应相关的综述却鲜有报道. 将RPCO反应分为还原型、氧化型以及氧化还原中性型三类, 并按照此分类逐一介绍了RPCO反应在天然产物全合成中的应用.

关键词: 天然产物全合成, 自由基化学, 串联反应, 自由基-极性交叉转化

Radical-polar crossover (RPCO) reactions are a class of cascade transformations that link radical and ionic intermediates, enabling the formation of multiple chemical bonds in a single step and thereby facilitating rapid increases in molecular complexity. Over the past few decades, a number of research groups have utilized RPCO reactions as key steps in the total synthesis of natural products, including terpenoids, alkaloids, lignans, and steroids. Despite these advances, compre- hensive reviews focusing on RPCO reactions remain limited. Applications of RPCO reactions in the total synthesis of natural products are systematically highlighted according to three categories: reduction type, oxidation type, and redox neutral type.

Key words: total synthesis of natural product, radical chemistry, cascade reaction, radical-polar crossover

引用此文

龙涛, 何述钟, 李超. 自由基-极性交叉转化反应在天然产物全合成中的研究进展[J]. 有机化学, 2025, 45(3): 748-763.

Tao Long, Shuzhong He, Chao Li. Research Progress on the Radical-Polar Crossover Reaction in Total Synthesis of Natural Products[J]. Chinese Journal of Organic Chemistry, 2025, 45(3): 748-763.

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图/表 16

图式1. 三种类型的RPCO反应

Scheme 1. Three types of RPCO reactions

图1. 一些利用RPCO反应合成的代表性天然产物

Figure 1. Some representative natural products synthesized via RPCO reactions

图式2. Castle课题组利用还原型RPCO构建季碳

Scheme 2. Constructionof a quaternary carbon via a reductive RPCO by Castle’s group

图式3. Castle课题组利用还原型RPCO实现acutumine的全合成

Scheme 3. Total synthesis of acutumine via a reductive RPCO achieved by Castle’s group

图式4. Pronin课题组利用还原型RPCO实现nodulisporic acid C的全合成

Scheme 4. Total synthesis of nodulisporic acid C via a reductive RPCO achieved by Pronin’s group

图式5. Pronin课题组利用还原型RPCO实现forskolin的全合成

Scheme 5. Total synthesis of forskolin via a reductive RPCO achieved by Pronin’s group

图式6. Pronin课题组利用还原型RPCO实现quassin的全合成

Scheme 6. Total synthesis of quassin via a reductive RPCO achieved by Pronin’s group

图式7. 李超课题组利用还原型RPCO构建双环[3.2.1]辛烷

Scheme 7. Construction of bicyclo[3.2.1]octanes via a reductive RPCO achieved by Li’s group

图式8. 李超课题组利用还原型RPCO实现11个二萜化合物的全合成

Scheme 8. Total synthesis of 11 diterpenoids via a reductive RPCO achieved by Li’s group

图式9. 李超课题组利用还原型RPCO实现marcocalyxoformin B的全合成

Scheme 9. Total synthesis of marcocalyxoformin B via a reductive RPCO achieved by Li’s group

图式10. Paquette课题组利用氧化型RPCO实现14-epiupial的全合成

Scheme 10. Total synthesis of 14-epiupial via an oxidative RPCO achieved by Paquette’s group

图式11. Heretsch课题组利用氧化型RPCO实现abifarine B的全合成

Scheme 11. Total synthesis of abifarine B via an oxidative RPCO achieved by Heretsch’s group

图式12. Heretsch课题组利用氧化型RPCO实现spirochensilide A/B的全合成

Scheme 12. Total synthesis of spirochensilide A/B via an oxidative RPCO achieved by Heretsch’s group

图式13. Murphy课题组利用氧化还原中性型RPCO实现aspidospermidine的全合成

Scheme 13. Total synthesis of aspidospermidine via a redox-neutral RPCO achieved by Murphy’s group

图式14. Sartillo-Piscill课题组利用氧化还原中性型RPCO实现cephalosporolide E/F的全合成

Scheme 14. Total synthesis of cephalosporolide E/F via a redox-neutral RPCO achieved by Sartillo-Piscil’s group

图式15. Lumb课题组利用氧化还原中性型RPCO实现4个DBCOD的全合成

Scheme 15. Total synthesis of DBCODs via a redox-neutral RPCO achieved by Lumb’s group

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