无金属参与的多烯选择性氯代反应

doi:10.6023/cjoc202510009

研究论文

无金属参与的多烯选择性氯代反应

王齐翔^a, 陈圣希^a, 王静^b, 陈栋^*,c, 鲍晓光^*,a, 吴新鑫^*,a

(^a苏州大学材料与化学化工学部江苏省有机合成重点实验室江苏苏州 215123)
(^b南京中医药大学附属苏州市中医医院江苏苏州 215000)
(^c河南工程学院材料工程学院河南省稀土复合材料国际联合实验室河南郑州 451191)

收稿日期:2025-10-15 修回日期:2025-11-28
基金资助:
苏州市“科教兴卫”青年科技项目(No. KJXW2022041),河南省高校科研重点项目(23A150052),河南省自然科学基金项目(242300421349)和河南省大学生创新创业训练项目(202511517010, 202511517022)资助项目.

Metal-Free Selective Chlorination of Polyenes

Wang Qixiang^a, Chen Shengxi^a, Wang Jing^b, Chen Dong^*,c, Bao Xiaoguang^*,a, Wu Xinxin^*,a

(^aKey Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, Jiangsu 215123)
(^bSuzhou TCM Hospital Affiliated to Nanjing University of Chinese Medicine, Suzhou, Jiangsu 215000)
(^cCollege of Material Engineering, Henan International Joint Laboratory of Rare Earth Composite Materials, Henan University of Engineering, Zhengzhou, Henan 451191)

Received:2025-10-15 Revised:2025-11-28
Contact: ^*E-mail: chendong@haue.edu.cn; xxwu99@suda.edu.cn
Supported by:
Project supported by the Suzhou "Revitalize Health through Science and Education" Youth Science and Technology Project (No. KJXW2022041), The Key Research Project of Higher Education Institutions of Henan Province (No. 23A150052), The Natural Science Foundation of Henan (No. 242300421349), The Innovation Training Program for College Students in Henan Province (No. 202511517010, 202511517022).

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摘要/Abstract

多烯（polyenes）作为具有连续共轭双键的特征性结构骨架,广泛存在于类胡萝卜素、维生素衍生物及大环内酯类抗生素等生物活性分子中. 然而,传统官能化方法面临区域选择性和化学选择性控制的关键挑战. 本研究发展了一种新型无金属催化体系, 以二氯碘苯(PhICl₂)为官能化试剂,通过调控添加物,成功实现了多烯分子的位点选择性多样性官能化. 本策略具有条件温和、官能团耐受性强及无金属参与等优势.

关键词: 多烯, 氯化反应, 高价碘化物, 自由基反应

Polyenes, featuring continuous conjugated double bonds, represent a fundamental structural motif widely found in biologically active molecules such as carotenoids, vitamin derivatives, and macrolide antibiotics. However, conventional functionalization strategies for polyenes often encounter major challenges in controlling regioselectivity and chemoselectivity. In this study, we developed a novel metal-free catalytic system employing iodobenzene dichloride (PhICl₂) as the functionalization reagent. By fine-tuning reaction additives, this method enables site-selective and diversified functionalization of polyene frameworks. The protocol offers several advantages, including mild reaction conditions, broad functional-group tolerance, and complete absence of transition metals.

Key words: polyenes, chlorination reaction, hypervalent iodine, radical reaction

引用此文

王齐翔, 陈圣希, 王静, 陈栋, 鲍晓光, 吴新鑫. 无金属参与的多烯选择性氯代反应[J]. 有机化学, doi: 10.6023/cjoc202510009.

Wang Qixiang, Chen Shengxi, Wang Jing, Chen Dong, Bao Xiaoguang, Wu Xinxin. Metal-Free Selective Chlorination of Polyenes[J]. Chinese Journal of Organic Chemistry, doi: 10.6023/cjoc202510009.

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