自由基介导的磷/硫中心手性构筑★

doi:10.6023/A26070270

综述

自由基介导的磷/硫中心手性构筑^★

杜天磊^a, 唐果^*,a,b, 龚磊^*,a

^a厦门大学化学化工学院福建省化学生物学重点实验室厦门 361005;
^b新疆大学化学学院碳基能源资源化学与利用重点实验室乌鲁木齐 830017

投稿日期:2026-07-28
作者简介:杜天磊,厦门大学化学化工学院, 博士研究生。2026年于上海大学取得硕士学位,之后,加入厦门大学龚磊教授课题组,攻读博士学位,研究兴趣为可见光诱导的自由基反应;唐果,厦门大学化学化工学院/新疆大学化学学院, 教授。1998 至 2001年, 在四川大学皮革工程专业, 师从周华龙教授,获得学士和硕士学位,然后在厦门大学师从赵玉芬院士,2004年,获得有机化学博士学位。主持三项国家自然科学基金项目,作为骨干参与了2项973项目以及赵玉芬院士的神州16号载人航天的空间站项目。2023年至今作为援疆干部在新疆大学化学学院工作。主要研究领域是有机磷物质的合成和应用,以通讯作者身份,在德国应用化学等国际知名期刊发表学术论文60多篇;龚磊,厦门大学化学化工学院教授、博导。先后于厦门大学获得学士、博士学位,在德国Marburg大学从事博士后研究。当前主要研究方向为：可见光催化、不对称合成。迄今共发表SCI论文90余篇,其中以通讯作者在Nat. Catal.、Nat. Synth.、J. Am. Chem. Soc.、Angew. Chem. Int. Ed.等发表论文70余篇;主持国家自然科学基金等项目15项;入选国家高层次青年人才、福建省杰出青年基金等人才项目;获Thieme Chemistry Journals Award、Asian Core Program Lectureship Award等奖项;担任中国化学会磷化学专委会委员等。^★“不对称协同催化”专辑

Radical-Mediated Construction of P- and S-Stereogenic Centers

Du Tianlei^a, Tang Guo^a,b,*, Gong, Lei^a,*

^aCollege of Chemistry and Chemical Engineering, Key Laboratory of Chemical Biology of Fujian Province, Xiamen University, Xiamen 361005;
^bKey Laboratory of Chemistry and Utilization of Carbon Based Energy Resources, College of Chemistry, Xinjiang University, Urumqi, 830017, China

Received:2026-07-28
Contact: * E-mail: t12g21@xmu.edu.cn; gongl@xmu.edu.cn
Supported by:
National Natural Science Foundation of China (22571265, 22371237). National Youth Talent Support Program for financial support.; Natural Science Foundation of Fujian Province of China (NO.2026H0002)

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摘要/Abstract

含有磷/硫中心手性的化合物广泛存在于手性配体及生物活性分子中,其不对称构筑是有机合成的重要研究方向。传统策略主要依赖离子型反应路径,往往需要化学计量的手性助剂、强碱或低温条件。近年来,自由基介导策略凭借温和的反应条件与独特的反应机制为该领域开辟了新途径,但因磷和硫中心自由基的构型翻转能垒差异大且不可预测,通过自由基途径构筑磷和硫中心手性缺乏有效的调控策略。本综述以手性控制机制为主线,系统总结了近五年来自由基策略构筑磷和硫中心手性的研究进展。其中,磷中心手性的构筑涵盖手性传递、动力学拆分与动态动力学拆分、光酶协同催化及光氧化还原协同不对称氧化等策略;硫中心手性的构筑涵盖手性传递、立体适应与去消旋化及手性诱导策略等。结合代表性实例和理论计算分析,本文阐述了相应的立体化学控制机制及其适用范围。最后,对该领域的挑战与前景进行了展望。

关键词: 自由基, 磷中心手性, 硫中心手性, 不对称合成, 协同催化

Chiral phosphorus- and sulfur-stereogenic compounds are widely found in chiral ligands and pharmaceutically active molecules, and their asymmetric construction represents an important research direction in synthetic organic chemistry. Traditional strategies mainly rely on ionic reaction pathways, often requiring stoichiometric chiral auxiliaries, strong bases, or low temperatures. In recent years, radical-mediated strategies have opened new avenues in this field, owing to their mild reaction conditions and distinctive mechanistic profiles. However, the construction of chiral phosphorus and sulfur centers via radical pathways remains challenging due to the lack of effective control strategies, as the configurational inversion barriers of phosphorus- and sulfur-centered radicals are not only substantially different but also unpredictable. This review systematically summarizes advances in the radical-based construction of phosphorus- and sulfur-stereogenic centers over the past five years, organized according to chiral control mechanisms. The construction of phosphorus stereocenters covers strategies including chirality transfer, kinetic resolution and dynamic kinetic resolution, photoenzymatic cooperative catalysis, and cooperative photoredox asymmetric oxidation; the construction of sulfur stereocenters covers chirality transfer, stereoadaptive and deracemization strategies, and chiral induction. By combining representative reaction examples and theoretical calculation analyses, the corresponding stereochemical control mechanisms and their applicable scope are elucidated. Finally, the current challenges and future prospects in this field are discussed.

Key words: radical, P-stereogenic center, S-stereogenic center, asymmetric synthesis, cooperative catalysis

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杜天磊, 唐果, 龚磊. 自由基介导的磷/硫中心手性构筑^★[J]. 化学学报, doi: 10.6023/A26070270.

Du Tianlei, Tang Guo, Gong, Lei. Radical-Mediated Construction of P- and S-Stereogenic Centers[J]. Acta Chimica Sinica, doi: 10.6023/A26070270.

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