Citation: Sheng Weijian, Jin Cheng'an, Shan Shang, Jia Yixia, Gao Jianrong. Metal-Free Polychloromethylation/Cyclization of N-Aryl Acrylamides[J]. Chinese Journal of Organic Chemistry, ;2016, 36(2): 325-329. doi: 10.6023/cjoc201509008 shu

Metal-Free Polychloromethylation/Cyclization of N-Aryl Acrylamides

1.
College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014

Corresponding author: Jia Yixia,
Received Date: 6 September 2015
Available Online: 23 October 2015
Fund Project: 国家自然科学基金(Nos. 21372202, 21522207) (Nos. 21372202, 21522207)新世纪优秀人才支持计划(No. NCET-12-1086) (No. NCET-12-1086)浙江省杰出青年科学基金(No. R14B020005)资助项目 (No. R14B020005)

A simple and metal-free radical addition/cyclization reaction of N-aryl acrylamides with CHCl₃or CH₂Cl₂ as radical source in the presence of benzoyl peroxide (BPO) as oxidant is developed, which affords polychloromethylated 2-oxindoles in moderate to good yields.
- benzoyl peroxide,
- polychloromethylation,
- radical,
- oxindole
1. [1]
  [1] For reviews, see: (a) Jensen, B. S. CNS Drug Rev. 2002, 8, 353. (b) Galliford, C. V.; Scheidt, K. A. Angew. Chem., Int. Ed. 2007, 46, 8748. (c) Singh, G. S.; Desta, Z. Y. Chem. Rev. 2012, 112, 6104. (d) Trost, B. M.; Xie, J.; Sieber, J. D. J. Am. Chem. Soc. 2011, 133, 20611. (e) Zhou, F.; Liu, Y.-L.; Zhou, J. Adv. Synth. Catal. 2010, 352, 1381.
2. [2]
  [2] For reviews, see: (a) Wu, T.; Mu, X.; Liu, G. Angew. Chem., Int. Ed. 2011, 50, 12578. (b) Mu, X.; Wu, T.; Wang, H.-Y.; Guo, Y.-L.; Liu, G. J. Am. Chem. Soc. 2012, 134, 878.
3. [3]
  [3] For Ag-catalyzed radical cascade synthesis of oxindoles, see: (a) Li, Y.-M.; Sun, M.; Wang, H.-L.; Tian, Q.-P.; Yang, S.-D. Angew. Chem., Int. Ed. 2013, 52, 3972. (b) Wang, H.; Guo, L.-N.; Duan, X.-H. Adv. Synth. Catal. 2013, 355, 2222. (c) Yuan, Y. Z.; Shen, T.; Wang, K.; Jiao, N. Chem. Asian J. 2013, 8, 2932. (d) Li, Y.-N.; Wang, J.-J.; Wei, X.-H.; Yang, S.-D. Chin. J. Org. Chem. 2015, 35, 638 (in Chinese). (李永红, 王君姣, 魏小红, 杨尚东, 有机化学, 2015, 35, 638.) For Cu-catalyzed radical cascade synthesis of oxindoles, see: (e) Li, Z.-J.; Zhang, Y.; Zhang, L.-Z.; Liu, Z.-Q. Org. Lett. 2014, 16, 382. (f) Li, J.; Wang, Z.-G.; Wu, N.-J.; Gao, G.; You, J.-S. Chem. Commun. 2014, 50, 15049. (g) Xu, Z.-B.; Yan, C.-X.; Liu, Z.-Q. Org. Lett. 2014, 16, 5670. For Fe-catalyzed radical cascade synthesis of oxindoles, see: (h) Wei, W.-T.; Zhou, M.-B.; Fan, J.-H.; Liu, W.; Song, R.-J.; Liu, Y.; Hu, M.; Xie, P.; Li, J.-H. Angew. Chem., Int. Ed. 2013, 52, 3638. (i) Lu, M.-Z.; Loh, T.-P. Org. Lett. 2014, 16, 4698. (j) Shen, T.; Yuan, Y.; Song, S.; Jiao, N. Chem. Commun. 2014, 50, 4115. For Mn-catalyzed radical cascade synthesis of oxindoles, see: (k) Li, X.-Q.; Xu, J.; Gao, Y.-Z.; Fang, H.; Tang, G.; Zhao, Y.-F. J. Org. Chem. 2015, 80, 2621.
4. [4]
  [4] For the metal-free oxidative difunctionalization of alkenes leading to oxindoles via a radical process, see: (a) Wu, T.; Zhang, H.; Liu, G. Tetrahedron 2012, 68, 5229. (b) Zhou, M.-B.; Song, R.-J.; Ouyang, X.-H.; Liu, Y.; Wei, W.-T.; Deng, G.-B.; Li, J.-H. Chem. Sci. 2013, 4, 2690. (c) Meng, Y.; Guo, L.-N.; Wang, H.; Duan, X.-H. Chem. Commun. 2013, 49, 7540. (d) Matcha, K.; Narayan, R.; Antonchick, A. P. Angew. Chem., Int. Ed. 2013, 52, 7985. (e) Li, X.; Xu, X.; Hu, P.; Xiao, X.; Zhou, C. J. Org. Chem. 2013, 78, 7343. (f ) Shen, T.; Yuan Y.-Z.; Jiao, N. Chem. Commun. 2014, 50, 554. (g) Li, Y. M.; Shen, Y. H.; Chang, K. J.; Yang, S. D. Tetrahedron 2014, 70, 1991.
5. [5]
  [5] (a) Dneprovskii, A. S.; Kasatochkin, A. N.; Boyarskii, V. P.; Ermoshkin, A. A.; Yakovlev, A. A. Russ. J. Org. Chem. 2006, 42, 1120. (b) Ashby, E. C.; Coleman, D. J. Org. Chem. 1987, 52, 4554.
6. [6]
  [6] Tian, Y.-F., Liu, Z.-Q. RSC Adv. 2014, 4, 64855.
7. [7]
  [7] Liu, Y.; Zhang, J. L.; Song, R. J.; Li, J. H. Org. Chem. Front. 2014, 1, 1289.
8. [8]
  [8] (a) A. Pinto, Y. Jia, L. Neuville, J. Zhu, Chem. Eur. J. 2007, 13, 961. (b) Xie, J.; Xu, P.; Li, H.; Xue, Q.; Jin, H.; Cheng, Y.; Zhu, C. Chem. Commun. 2013, 49, 5672. (c) Ayitou, A. A.-L.; Sivaguru, J. Chem. Commun. 2011, 47, 2568.
1. [1]
  Lei Shi . Nucleophilicity and Electrophilicity of Radicals. University Chemistry, 2024, 39(11): 131-135. doi: 10.3866/PKU.DXHX202402018
2. [2]
  Baitong Wei , Jinxin Guo , Xigong Liu , Rongxiu Zhu , Lei Liu . Theoretical Study on the Structure, Stability of Hydrocarbon Free Radicals and Selectivity of Alkane Chlorination Reaction. University Chemistry, 2025, 40(3): 402-407. doi: 10.12461/PKU.DXHX202406003
3. [3]
  Danqing Wu , Jiajun Liu , Tianyu Li , Dazhen Xu , Zhiwei Miao . Research Progress on the Simultaneous Construction of C—O and C—X Bonds via 1,2-Difunctionalization of Olefins through Radical Pathways. University Chemistry, 2024, 39(11): 146-157. doi: 10.12461/PKU.DXHX202403087
4. [4]
  Min LIU , Huapeng RUAN , Zhongtao FENG , Xue DONG , Haiyan CUI , Xinping WANG . Neutral boron-containing radical dimers. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 123-130. doi: 10.11862/CJIC.20240362
5. [5]
  Liangzhen Hu , Li Ni , Ziyi Liu , Xiaohui Zhang , Bo Qin , Yan Xiong . A Green Chemistry Experiment on Electrochemical Synthesis of Benzophenone. University Chemistry, 2024, 39(6): 350-356. doi: 10.3866/PKU.DXHX202312001
6. [6]
  Tongyan Yu , Pan Xu . Visible-Light Photocatalyzed Radical Rearrangement Reaction. University Chemistry, 2025, 40(7): 169-176. doi: 10.12461/PKU.DXHX202409070
7. [7]
  Jiajia Li , Xiangyu Zhang , Zhihan Yuan , Zhengyang Qian , Jian Zhu . 3D Printing Based on Photo-Induced Reversible Addition-Fragmentation Chain Transfer Polymerization. University Chemistry, 2024, 39(5): 11-19. doi: 10.3866/PKU.DXHX202309073
8. [8]
  Zijian Zhao , Yanxin Shi , Shicheng Li , Wenhong Ruan , Fang Zhu , Jijun Jiang . A New Exploration of the Preparation of Polyacrylic Acid by Free Radical Polymerization Based on the Concept of Green Chemistry. University Chemistry, 2024, 39(5): 315-324. doi: 10.3866/PKU.DXHX202311094
9. [9]
  .
  CCS Chemistry | 超分子活化底物为自由基促进高效选择性光催化氧化
  . CCS Chemistry, 2025, 7(10.31635/ccschem.025.202405229): -.
10. [10]
  Zhongyan Cao , Shengnan Jin , Yuxia Wang , Yiyi Chen , Xianqiang Kong , Yuanqing Xu . Advances in Highly Selective Reactions Involving Phenol Derivatives as Aryl Radical Precursors. University Chemistry, 2025, 40(4): 245-252. doi: 10.12461/PKU.DXHX202405186
11. [11]
  Liyang ZHANG , Dongdong YANG , Ning LI , Yuanyu YANG , Qi MA . Crystal structures, luminescent properties and Hirshfeld surface analyses of three cadmium(Ⅱ) complexes based on 2-(3-(pyridin-2-yl)-1H-pyrazol-1-yl)benzoate. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1943-1952. doi: 10.11862/CJIC.20240079
12. [12]
  Yuan GAO , Yiming LIU , Chunhui WANG , Zhe HAN , Chaoyue FAN , Jie QIU . A hexanuclear cerium oxo cluster stabilized by furoate: Synthesis, structure, and remarkable ability to scavenge hydroxyl radicals. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 491-498. doi: 10.11862/CJIC.20240271
13. [13]
  Dan Liu . 可见光-有机小分子协同催化的不对称自由基反应研究进展. University Chemistry, 2025, 40(6): 118-128. doi: 10.12461/PKU.DXHX202408101
14. [14]
  Xinxin Wu . 基础有机化学教学中自由基重排反应的课程设计及其课程思政元素的融入. University Chemistry, 2025, 40(6): 316-325. doi: 10.12461/PKU.DXHX202408055
15. [15]
  Yihui Song , Shangshang Qin , Kai Wu , Chengyun Jin , Bin Yu . 生物化学在高水平创新型药学人才培养中的交叉融合应用——以去甲基化酶LSD1抑制剂的活性评价为例. University Chemistry, 2025, 40(6): 341-352. doi: 10.12461/PKU.DXHX202406018
16. [16]
  Lina Feng , Guoyu Jiang , Xiaoxia Jian , Jianguo Wang . Application of Organic Radical Materials in Biomedicine. University Chemistry, 2025, 40(4): 253-260. doi: 10.12461/PKU.DXHX202405171
17. [17]
  Zhaoyang WANG , Chun YANG , Yaoyao Song , Na HAN , Xiaomeng LIU , Qinglun WANG . Lanthanide(Ⅲ) complexes derived from 4′-(2-pyridyl)-2, 2′∶6′, 2″-terpyridine: Crystal structures, fluorescent and magnetic properties. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1442-1451. doi: 10.11862/CJIC.20240114
18. [18]
  Aiyi Xin , Jiawei Li , Xinyang Ran , Chuanjiang Fu , Zhiguo Wang . Collaborative Science and Education Based Experimental Design in Organic Chemistry: A Case Study of the Nucleophilic Substitution Reaction of 2-Hydroxymethyl-4,6-Di-Tert-Butylphenol. University Chemistry, 2025, 40(5): 366-375. doi: 10.12461/PKU.DXHX202407031
19. [19]
  Caixia Lin , Ting Liu , Zhaojiang Shi , Hong Yan , Keyin Ye , Yaofeng Yuan . Innovative Experiment of Electrochemical Dearomative Spirocyclization of N-Acyl Sulfonamides. University Chemistry, 2025, 40(4): 359-366. doi: 10.12461/PKU.DXHX202406107
20. [20]
  Tao Cao , Fang Fang , Nianguang Li , Yinan Zhang , Qichen Zhan . Green Synthesis of p-Hydroxybenzonitrile Catalyzed by Spinach Extracts under Red-Light Irradiation: Research and Exploration of Innovative Experiments for Pharmacy Undergraduates. University Chemistry, 2024, 39(5): 63-69. doi: 10.3866/PKU.DXHX202309098

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(1150)
HTML views(157)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142