Metal-Free Selective Chlorination of Polyenes

doi:10.6023/cjoc202510009

Chinese Journal of Organic Chemistry ›› 2026, Vol. 46 ›› Issue (4): 1750-1762.DOI: 10.6023/cjoc202510009 Previous Articles Next Articles

ARTICLES

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省稀土复合材料国际联合实验室郑州 451191

收稿日期:2025-10-15 修回日期:2025-11-28 发布日期:2026-01-06
通讯作者: 陈栋, 鲍晓光, 吴新鑫
基金资助:
苏州市“科教兴卫”青年科技(KJXW2022041); 河南省高校科研重点(23A150052); 河南省自然科学基金(242300421349); 河南省大学生创新创业训练(202511517010); 河南省大学生创新创业训练(202511517022)

Metal-Free Selective Chlorination of Polyenes

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

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

Received:2025-10-15 Revised:2025-11-28 Published:2026-01-06
Contact: Dong Chen, Xiaoguang Bao, Xinxin Wu
Supported by:
Suzhou “Revitalize Health through Science and Education” Youth Science and Technology Project(KJXW2022041); Key Research Project of Higher Education Institutions of Henan Province(23A150052); Natural Science Foundation of Henan Province(242300421349); Innovation Training Program for College Students in Henan Province(202511517010); Innovation Training Program for College Students in Henan Province(202511517022)

1. .pdf(6744KB)

Abstract

Polyenes, characterized by continuous conjugated double bonds, represent a fundamental structural motif widely present 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, a novel metal-free catalytic system employing iodobenzene dichloride (PhICl₂) as the functionalization reagent was developed. 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

Cite this article

Qixiang Wang, Shengxi Chen, Jing Wang, Dong Chen, Xiaoguang Bao, Xinxin Wu. Metal-Free Selective Chlorination of Polyenes[J]. Chinese Journal of Organic Chemistry, 2026, 46(4): 1750-1762.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 7

Scheme 1. Overview of polyenes and their selective functionalization

Entry^a	Base (equiv.)	Additive	Yield^b/% of 2a-1/2a-3/2a-4
1^c	—	—	63/13/0
2^d	—	—	26/0/28
3	Pyridine (1.0)	—	19/0/56
4	Pyridine (2.0)	—	11/0/64
5	Pyridine (3.0)	—	9/0/88
6	Pyridine (4.0)	—	21/0/59
7	—	TBABF₄	42/11/0
8	Pyridine (3.0)	TBABF₄	0/0/92^e
9	Py•HCl (3.0)	TBABF₄	0/0/95^e
10	4-Br-Py•HCl (3.0)	TBABF₄	0/0/96^e
11^f	4-Br-Py•HCl (3.0)	TBABF₄	0/0/96^e

Table 1. Optimization of reaction conditions

Substrate	Product	Substrate	Product

Table 2. Investigation of substrate scope

Scheme 2. Investigation of functionalities a Reaction conditions: 1b (0.1 mmol, 1.0 equiv.), PhICl2 (0.11 mmol, 1.1 equiv.) in MeOH (4 mL) were stirred at r.t. for 1.5 h under N2. b Reaction conditions: 1b (0.1 mmol, 1.0 equiv.), PhICl2 (0.11 mmol, 1.1 equiv.) in DMF (4 mL) were stirred at r.t. for 1.5 h under N2. c Reaction conditions: 1b (0.1 mmol, 1.0 equiv.), PhICl2 (0.11 mmol, 1.1 equiv.) in MeCN/H2O (V∶V=1∶1, 4 mL) were stirred at r.t. for 1.5 h under N2.

Scheme 3. Product transformations

Scheme 4. Mechanistic studies

Scheme 5. Proposed reaction mechanism

References 16

[1]	(a) Deng, Q.; Li, Y.; He, W.; Chen, T.; Liu, N.; Ma, L.; Qiu, Z.; Shang, Z.; Wang, Z. Nature 2025, 640, 743.
	(b) Molloy, J. J.; Schäfer, M.; Wienhold, M.; Morack, T.; Daniliuc, C. G.; Gilmour, R. Science 2020, 369, 302.
[2]	Harrison, E. H. Nutrients 2022, 14, 1411.
[3]	(a) Thai, L.; Rush, J. S.; Devarenne, T.; Rodgers, D. L.; Chappell, J.; Waechter, C. J. Proc. Natl. Acad. Sci. U. S. A. 1999, 96, 13080.
	(b) Liu, M.; Wang, Z.; Qin, C.; Cao, H.; Kong, L.; Liu, T.; Jiang, S.; Ma, L.; Liu, X.; Ren, W.; Ma, W. J. Agric. Food Chem. 2024, 72, 11429.
[4]	Lacombe, R. J. S.; Chouinard-Watkins, R.; Bazinet, R. P. Mol. Asp. Med. 2018, 64, 109.
[5]	Bruno, F.; Camuso, S.; Capuozzo, E.; Canterini, S. Antibiotics 2023, 12, 122.
[6]	Snyder, S. A.; Treitler, D. S.; Brucks, A. P. J. Am. Chem. Soc. 2010, 132, 14303.
[7]	Sakakura, A.; Ukai, A.; Ishihara, K. Nature 2007, 445, 900.
[8]	(a) Waser, J.; González-Gómez, J. C.; Nambu, H.; Huber, P.; Carreira, E. M. Org. Lett. 2005, 7, 4249.
	(b) Vrubliauskas, D.; Vanderwal, C. D. Angew. Chem., Int. Ed. 2020, 59, 6115.
[9]	(a) Smith, D. M.; Pulling, M. E.; Norton, J. R. J. Am. Chem. Soc. 2007, 129, 770.
	(b) Tian, L.; Bhat, M.; Chen, X.-Y.; Li, Y.-L.; Shu, W. Tetrahedron 2025, 185, 134835.
[10]	(a) Fokou, P. A.; Meier, M. A. J. Am. Chem. Soc. 2009, 131, 1664.
	(b) Sun, H.; Liang, Y. F.; Thompson, M. P.; Gianneschi, N. C. Prog. Polym. Sci. 2021, 120, 101427.
	(c) Starvaggi, F. A.; Suslick, B. A.; Xia, Y. ACS Macro Lett. 2024, 13, 296.
[11]	(a) Malcolmson, S.; Meek, S.; Sattely, E.; Schrock, R. R.; Hoveyda, A. H. Nature 2008, 456, 933.
	(b) Trost, B. M.; Min, C. Nat. Chem. 2020, 12, 568.
	(c) Crossley, S. W. M.; Barabe, F.; Shenvi, R. A. J. Am. Chem. Soc. 2014, 136, 16788.
	(d) Xiao, J.-X.; Li, F.-X.; Ren, S.-J.; Qu, J. Angew. Chem., Int. Ed. 2024, 63, e202403597.
[12]	Essayan, D. E.; Schubach, M. J.; Smoot, J. M.; Puri, T.; Pronin, S. V. J. Am. Chem. Soc. 2024, 146, 18224.
[13]	Reddy, G. S.; Corey, E. J. J. Am. Chem. Soc. 2025, 147, 1448.
[14]	Patra, T.; Arepally, S.; Seitz, J.; Wirth, T. Nat. Commun. 2024, 15, 6329.
[15]	Cresswell, A. J.; Eey, S. T.-C.; Denmark, S. E. Angew. Chem., Int. Ed. 2015, 54, 15642.
[16]	He, Y.; Tian, C.; An, Gu.; Li, G. Chin. Chem. Lett. 2024, 35, 108546.

无金属参与的多烯选择性氯代反应

Metal-Free Selective Chlorination of Polyenes

RichHTML

PDF

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

Fig. & Tab. 7

References 16

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Jingfei Zheng, Qiyan Lv, Kai Sun, Xiaolan Chen, Lingbo Qu, Jinquan Wang, Bing Yu. Recent Advances in Functionalization of 6-Azauracils via Radical Reactions [J]. Chinese Journal of Organic Chemistry, 2026, 46(4): 1603-1620.
[2]	Shizheng Liu, Mingyu Dou, Yu Cui, Jianmin Dou, Wenting Wei. Research Progress on Radical Selenosulfonylation [J]. Chinese Journal of Organic Chemistry, 2026, 46(4): 1621-1634.
[3]	Yuqing Zhao, Xianjin Zhu, Lingyu Shi, Mingyu Wei, Zihan Xu, Yongjia Shi, Xufeng Li, Daoshan Yang. Research Progress on the Ring-Opening Functionalization of Cyclic Sulfonium Salts [J]. Chinese Journal of Organic Chemistry, 2026, 46(4): 1572-1602.
[4]	Shan Yang, Yasu Chen, Chen Zhu. Construction of N-Fused Heteroarenes via Radical-Mediated Functional Group Migration-Cyclization [J]. Chinese Journal of Organic Chemistry, 2026, 46(4): 1739-1749.
[5]	Shaohua Wu, Fan Gong, Zhu Cao, Qinghai Deng. Recent Advances in Hypervalent Iodine Mediated Radical Fluoroalkylative Difunctionalization of Alkenes [J]. Chinese Journal of Organic Chemistry, 2026, 46(4): 1390-1427.
[6]	Weiwen Ji, Jian Jin. Ligand-to-Metal Charge Transfer-Driven Photoinduced Metal-Catalyzed Decarboxylative Transformation of Aryl Carboxylic Acids [J]. Chinese Journal of Organic Chemistry, 2026, 46(4): 1320-1329.
[7]	Yong Liu, Juan Li, Lingfan Wang, Baotong Huang, Lingzi Peng, Jin Song, Chang Guo. Electrochemically Driven Radical Alkylation of Alkenes with 1,3-Dicarbonyl Compounds [J]. Chinese Journal of Organic Chemistry, 2026, 46(4): 1659-1667.
[8]	Bin Zhang, Wenjing Xiao, Jiarong Chen. Controlled Generation and Transformations of Alkene Radical Anions [J]. Chinese Journal of Organic Chemistry, 2026, 46(4): 1181-1204.
[9]	Yingjie Liu, Laisheng Min, Ruirong Yang, Dongxue Song, Rui Peng, Deqiang Liang. CuI-Catalyzed C—C Bond Coupling Reaction for the Construction of 2-Carbonyl-1,4-diketones [J]. Chinese Journal of Organic Chemistry, 2026, 46(2): 603-611.
[10]	Yongbo Tan, Hongbo Shu, Huawen Huang. Recent Advances in Photo-Induced Oxindole Formation from N-Arylacrylamides [J]. Chinese Journal of Organic Chemistry, 2025, 45(6): 2086-2108.
[11]	Shunxi Li, Lixu You, Yulong Li, Wei Shu. Recent Progress on Light-Mediated C—N Bond-Forming Processes from Ammonia and Equivalents [J]. Chinese Journal of Organic Chemistry, 2025, 45(5): 1460-1477.
[12]	Haoyan Wu, Mingyue He, Jun'an Ma, Faguang Zhang. Recent Advances in Photochemical Reactions Enabled by Triarylamine [J]. Chinese Journal of Organic Chemistry, 2025, 45(5): 1634-1643.
[13]	Tianpeng Ling, Haitao Qin, Feng Liu. Recent Advances in Enantioselective Radical Reactions of C(sp³)—H Bond [J]. Chinese Journal of Organic Chemistry, 2025, 45(2): 498-515.
[14]	Yu'nan Zhu, Weikang Jiao, Xuebai Wei, Chunhua Chen, Dongliang Mo. Recent Progress in Radical Arylation Reaction Involving Diaryliodonium Salts [J]. Chinese Journal of Organic Chemistry, 2025, 45(10): 3672-3690.
[15]	Zijie Li, Zheng Hao, Shengyuan Yang, Wenchao Yang, Tao Jin. Recent Advances in the Radical Reactions of Dihydroquinazolinone Derivatives [J]. Chinese Journal of Organic Chemistry, 2025, 45(10): 3644-3654.