胺-硼烷自由基的产生及其在有机合成中的应用

doi:10.6023/A25120413

化学学报 ›› 2026, Vol. 84 ›› Issue (3): 385-408.DOI: 10.6023/A25120413 上一篇下一篇

综述

胺-硼烷自由基的产生及其在有机合成中的应用

廖文权^a, 丁秋平^a^,^*(), 张俊^b^,^*(), 吴劼^b^,^c^,^*()

^a 江西师范大学化学与材料学院南昌 330022
^b 台州学院医药化工学院&高等研究院台州 318000
^c 中国科学院上海有机化学研究所金属有机化学国家重点实验室上海 200032

投稿日期:2025-12-23 发布日期:2026-01-26
通讯作者: 丁秋平, 张俊, 吴劼

作者简介:

廖文权, 男, 江西师范大学化学与材料学院2024级研究生, 研究方向为: 金属催化的自由基反应.

丁秋平, 教授、博士生导师. 于2009年6月获得复旦大学博士学位, 之后分别曾在中科院理化所以及美国斯克利普斯研究所从事博士后、访问学者工作.任职于江西师范大学化学与材料学院, 研究方向为: 基于绿色合成方法(多组分串联法、碳氢键活化法)合成具有潜在生物活性的功能有机小分子. 目前, 在J. Am. Chem. Soc.; Chem. Soc. Rev.; ACS Catal.; Green Chem.; Org. Lett.; Green Synth. Catal.; Chem. Commun.; J. Org. Chem.等国际核心期刊发表SCI论文130余篇, 授权专利10项.

张俊, 副教授, 本科毕业于河南大学; 博士毕业于复旦大学(导师: 吴劼教授); 2021年7月入职台州学院高等研究院, 主要从事自由基反应研究.

吴劼, 教授、博士生导师. 于2000年6月获得中科院上海有机化学研究所博士学位, 之后分别先后在哈佛大学、洛克菲勒大学艾伦·戴蒙德艾滋病研究中心、VivoQuest, Inc. (纽约)从事博士后、访问学者、研究员工作. 2004年回国进入复旦大学化学系担任副教授, 2006年晋升为教授, 博士生导师. 2019年加入台州学院医药化工学院, 主要从事有机合成、药物化学及相关研究工作. 独立工作以来已在Nat. Commun.; J. Am. Chem. Soc.; Angew. Chem. Int. Ed.; Chem. Soc. Rev.等国际核心期刊发表SCI论文400余篇, 参与编写专著四本, 独立撰写专著一本, 获得美国发明专利2项, 中国发明专利30余项.

基金资助:
项目受国家自然科学基金(22201200); 浙江省自然科学基金(LZ23B020001)

Amine-Ligated Boryl Radicals: Generation and Synthetic Applications

Liao Wenquan^a, Ding Qiuping^a^,^*(), Zhang Jun^b^,^*(), Wu Jie^b^,^c^,^*()

^a College of Chemistry and Materials, Jiangxi Normal University, Nanchang 330022, China
^b School of Pharmaceutical and Chemical Engineering & Institute for Advanced Studies, Taizhou University, Taizhou 318000, China
^c State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China

Received:2025-12-23 Published:2026-01-26
Contact: Ding Qiuping, Zhang Jun, Wu Jie
Supported by:
National Natural Science Foundation of China(22201200); Natural Science Foundation of Zhejiang Province(LZ23B020001)

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摘要/Abstract

根据电子结构特征, 硼自由基主要分为中性硼自由基与路易斯碱配位的硼自由基两类. 后者通过配位策略显著提高了硼自由基的稳定性与可控性, 是当前有机硼化学领域的研究热点. 其中, 胺配位的物种电子结构独特: 自旋密度主要定域于硼, 亲核性突出, 在合成转化中具有独特的应用潜力. 然而, 胺-硼烷自由基在早期因产生方法有限, 其应用受到了很大限制. 近五年, 得益于自由基化学的快速发展, 胺-硼烷自由基的产生方式和应用取得重要突破. 本文聚焦于胺-硼烷自由基, 内容分为四个部分, 依次介绍其参与的: (1)氢原子转移反应; (2)自由基加成反应; (3)卤原子转移反应; (4)自由基取代反应. 最后, 本文对该方向的未来发展前景进行了简要展望.

关键词: 胺-硼烷, 硼自由基, 硼基化, 氢原子转移, 卤原子转移

While radical chemistry has achieved significant progress over the past few decades, the development of boron-centered radical chemistry remains relatively delayed. Generally, boron radicals can be classified into two main categories based on their electronic structures: neutral boron radicals and Lewis base-ligated boryl radicals. Neutral boron radicals feature only five valence electrons, making them highly electron-deficient and extremely unstable species. This high electron deficiency and instability pose significant challenges to their direct application. In contrast, Lewis base-ligated boryl radicals (with seven electrons) exhibit markedly enhanced stability and more controllable reactivity, which has made them a current focus in boron chemistry. To date, numerous synthetic transformations have been developed using boryl radicals ligated by various Lewis bases such as N-heterocyclic carbenes, organophosphines, pyridines, alcohols, and amines. The generation and reactivity of these radicals are significantly influenced by the electronic and steric properties of their Lewis base ligands. Among them, amine-ligated boryl radicals, in which spin density is predominantly localized on the boron center, exhibit strong nucleophilic character and thus demonstrate unique reactivity. However, the early reliance on methods such as UV photolysis of peroxides or thermal decomposition of azo compounds to generate alkoxyl radicals, which subsequently promoted the formation of amine-ligated boryl radicals, posed a constraint on their widespread applications. In the past five years, the emergence of new theories and technologies in radical chemistry has enabled the expansion of methods for generating amine-ligated boryl radicals. These include novel catalytic systems (e.g., visible-light photocatalysis, visible-light-metal cooperative catalysis, photoelectrocatalysis) and new boryl radical precursors (e.g., amine-carboxyborane). This progress has vigorously promoted their widespread application in diverse synthetic transformations. This manuscript reviews advances in the generation of amine-ligated boryl radicals and summarizes their synthetic applications. It is divided into four sections according to the distinct reaction mechanisms involved: (1) hydrogen atom transfer; (2) radical addition reactions; (3) halogen atom transfer; (4) radical replacement. Finally, a brief outlook on future developments is provided.

Key words: amine-boranes, boryl radicals, borylation, hydrogen atom transfer, halogen atom transfer

引用此文

廖文权, 丁秋平, 张俊, 吴劼. 胺-硼烷自由基的产生及其在有机合成中的应用[J]. 化学学报, 2026, 84(3): 385-408.

Liao Wenquan, Ding Qiuping, Zhang Jun, Wu Jie. Amine-Ligated Boryl Radicals: Generation and Synthetic Applications[J]. Acta Chimica Sinica, 2026, 84(3): 385-408.

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图/表 26

图式1. 硼中心自由基以及路易斯碱配位的硼烷

Scheme 1. Boron-centered radicals and Lewis base-ligated boranes

图式2. 胺-硼烷催化合成环氧丙烷化合物

Scheme 2. Synthesis of propylene oxide compounds using amine-boranes

图式3. 胺-硼烷催化合成取代的烯丙醇类产物以及多酯基化产物

Scheme 3. Synthesis of substituted allylic alcohols and multi-ester functionalized products using amine-boranes

图式4. 胺-硼烷催化实现未活化烯烃氢烷基化

Scheme 4. Hydroalkylation of unactivated alkenes enabled by amine-boranes

图式5. 光催化三甲基胺-硼烷参与的氮杂环的选择性硼基化反应

Scheme 5. Photocatalytic regioselective borylation of azines enabled by trimethylamine-borane

图式6. 胺-硼烷参与的腺苷及腺嘌呤衍生物的区域选择性硼基化

Scheme 6. Regioselective borylation of adenosine and adenine derivatives using amine-boranes

图式7. 光/电催化三甲基胺-硼烷参与的缺电子(杂)芳环的选择性硼基化

Scheme 7. Photoelectrocatalytic regioselective borylation of electron-deficient (hetero)arenes using trimethylamine-borane

图式8. 光/HAT/钴协同催化胺-硼烷参与的脱氢硼基化反应

Scheme 8. Photo/HAT/Cobalt cooperative catalysis for dehydrogenative borylation using amine-boranes

图式9. 光催化三甲基胺-羧基硼烷参与C(sp3)—B键的构建(Leonori’s work)

Scheme 9. Photocatalytic C(sp3)—B bond formation with trimethylamine-carboxyborane (Leonori’s work)

图式10. 光催化三甲基胺-羧基硼烷参与C(sp3)—B键的构建(Xu’s work)

Scheme 10. Photocatalytic C(sp3)—B bond formation with trimethylamine-carboxyborane (Xu’s work)

图式11. 光催化三甲基胺-羧基硼烷参与的脱氟硼基化反应

Scheme 11. Photocatalytic defluorinative borylation using trimethylamine-carboxyborane

图式12. 光催化三甲基胺-羧基硼烷参与C(sp)—B键的构建

Scheme 12. Photocatalytic C(sp)—B bond formation with trimethylamine-carboxyborane

图式13. 光催化三甲基胺-羧基硼烷参与的多氟芳烃的C—F键硼基化

Scheme 13. Photocatalytic C—F bond borylation of polyfluoroarenes with trimethylamine-carboxyborane

图式14. 光催化三甲基胺-羧基硼烷参与的脱氰氘代

Scheme 14. Photocatalytic decyanative deuteration with trimethylamine-carboxyborane

图式15. 光催化三甲基胺-羧基硼烷参与的脱氰基自由基加成

Scheme 15. Photocatalytic decyanative radical addition with trimethylamine-carboxyborane

图式16. 三甲基胺-硼烷参与的烯烃的二氟甲基化氢化反应

Scheme 16. Hydrodifluoromethylation of alkenes enabled by trimethylamine-borane

图式17. 奎宁环-硼烷参与的烯烃二氟烷基化氢化反应

Scheme 17. Hydrodifluoroalkylation of alkenes enabled by quinuclidine-borane

图式18. 三甲基胺-硼烷参与的烯烃磺酰化肟化

Scheme 18. Sulfamoyl-oximation of alkenes enabled by trimethylamine-borane

图式19. 三甲基胺-羧基硼烷参与的环丙烷化反应

Scheme 19. Cyclopropanation reactions with trimethylamine-carboxyboranes

图式20. 三甲基胺-羧基硼烷介导的烯烃的氢化官能团化

Scheme 20. Hydrofunctionalization of alkenes enabled by trimethylamine-carboxyborane

图式21. 三甲基胺-硼烷介导的烷基卤代物的炔基化

Scheme 21. Alkynylation of alkyl halides enabled by trimethylamine-borane

图式22. 三甲基胺-硼烷促进的C(sp2)—Br的活化

Scheme 22. Activation of C(sp2)—Br bonds enabled by trimethylamine-borane

图式23. 三甲基胺-硼烷介导的烷基卤化物的芳基化

Scheme 23. Arylation of alkyl halides enabled by trimethylamine-borane

图式24. 三甲基胺-硼烷介导的烷基溴代物与芳基溴的交叉偶联

Scheme 24. Cross-coupling of alkyl bromides with aryl bromides mediated by trimethylamine-borane

图式25. 三甲基胺-硼烷介导的卤代烷烃与酰胺的偶联

Scheme 25. Cross-coupling of alkyl halides with amides mediated by trimethylamine-borane

图式26. 三乙基胺-硼烷促进的C(sp3)—Cl键的活化

Scheme 26. Activation of alkyl chlorides enabled by triethylamine-borane

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胺-硼烷自由基的产生及其在有机合成中的应用

Amine-Ligated Boryl Radicals: Generation and Synthetic Applications

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