Citation: Tang Nana, Shao Xin, Wang Mingyang, Wu Xinxin, Zhu Chen. Sulfonyl Chlorides Mediated Alkynylation of Non-activated Alkenes via Distal Alkynyl Group Migration[J]. Acta Chimica Sinica, ;2019, 77(9): 922-926. doi: 10.6023/A19050158 shu

Sulfonyl Chlorides Mediated Alkynylation of Non-activated Alkenes via Distal Alkynyl Group Migration

Tang Nana ^a,† ,
Shao Xin ^a,† ,
Wang Mingyang ^a ,
Wu Xinxin ^a ,
Zhu Chen ^a,b,,

a.
College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, Jiangsu 215123
b.
Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032

Corresponding author: Zhu Chen, chzhu@suda.edu.cn
Received Date: 1 May 2019
Available Online: 4 September 2019
Fund Project: Project supported by the National Natural Science Foundation of China (No. 21722205)the National Natural Science Foundation of China 21722205

Figures(4)

Radical-mediated difunctionalization of alkenes through the remote functional group migration (FGM) process paves an ingenious avenue for simultaneous cleavage and reconstruction of C-C bonds. Recently, our group has systematically disclosed the strategy of remote FGM for radical-mediated difunctionalization of unactivated alkenes. A portfolio of functional groups including cyano, heteroaryl, alkynyl, oximino, and carbonyl showcase the migratory aptitude, leading to new C-C bonds under radical conditions. Meanwhile, a series of other chemical bonds such as C-C, C-N, C-P, C-Si, and C-S are readily constructed in the reaction. Considering the synthetic utility and flexible transformation of alkynes, the radical alkynylation of unactivated alkenes via remote alkynyl migration we firstly reported provides an efficient approach for the incorporation of alkynes and has received considerable attention. On the other hand, fluorine-and sulfonyl-containing molecules play vital roles in organic and medicinal chemistry owing to their important chemical and physical characters. Therefore, the concomitant introduction of an alkynyl and a trifluoromethyl/sulfonyl group into one molecule is of great synthetic value. Herein we report a useful method for carbo-trifluoroalkylation/sulfonylation of unactivated olefins. The addition of extrinsic radical to alkene triggers the intramolecular FGM via a five-membered transition state along with a cascade of bond fission and formation. The typical procedure is as follows:a mixture of propargyl alcohol 1, sulfonyl chloride, fac-Ir(ppy)₃, and base is loaded in a flame-dried reaction vial which is subjected to evacuation/flushing with nitrogen three times. Solvent is added to the mixture via syringe and the mixture is then stirred at 25℃ until the starting material is consumed monitored by TLC. The mixture is concentrated, and purified by flash column chromatography on silica gel (eluent:petroleum ether/ethyl acetate) to give the product.
- alkynylation,
- trifluoromethylation,
- carbosulfonylation,
- alkene difunctionalization,
- functional group migration
1. [1]
2. [2]
3. [3]
  For selected examples of remote FGM from other groups: (a) Thaharn, W.; Soorukram, D.; Kuhakarn, C.; Tuchinda, P.; Reutrakul, V.; Pohmakotr, M. Angew. Chem. Int. Ed. 2014, 53, 2212; (b) Li, L.; Li, Z.-L.; Wang, F.-L.; Guo, Z; Cheng, Y.-F.; Wang, N.; Dong, X.-W.; Fang, C.; Liu, J.; Hou, C.; Tan, B.; Liu, X.-Y. Nat. Commun. 2016, 7, 13852; (c) Li, Z.-L.; Li, X.-H.; Wang, N.; Yang, N.-Y.; Liu, X.-Y. Angew. Chem. Int. Ed. 2016, 55, 15100; (d) Li, L.; Li, Z.-L.; Gu, Q.-S.; Wang, N.; Liu, X.-Y. Sci. Adv. 2017, 3, e1701487; (e) Wang, N.; Li, L.; Li, Z.-L.; Yang, N.-Y.; Guo, Z.; Zhang, H.-X.; Liu, X.-Y. Org. Lett. 2016, 18, 6026; (f) Tang, X.; Studer, A. Angew. Chem. Int. Ed. 2018, 57, 814; (g) Wang, H.; Xu, Q.; Yu, S. Org. Chem. Front. 2018, 5, 2224; (h) He, Y.; Wang, Y.; Gao, J.; Zeng, L.; Li, S.; Wang, W.; Zheng, X.; Zhang, S.; Gu, L.; Li, G. Chem. Commun. 2018, 54, 7499; (i) Gu, L.; Gao, Y.; Ai, X.; Jin, C.; He, Y.; Li, G.; Yuan, M. Chem. Commun. 2017, 53, 12946; (j) Wei, X.-J.; No l, T. J. Org. Chem. 2018, 83, 11377.
4. [4]
  Xu, Y.; Wu, Z.; Jiang, J.; Ke, Z.; Zhu, C. Angew. Chem. Int. Ed. 2017, 56, 4545. doi: 10.1002/anie.201700413
5. [5]
  For selected examples of alkynyl migration: (a) Tang, X.; Studer, A. Chem. Sci. 2017, 8, 6888; (b) Liu, J.; Li, W.; Xie, J.; Zhu, C. Org. Chem. Front. 2018, 5, 797; (c) Zhao, Q.; Ji, X.-S.; Gao, Y.-Y.; Hao, W.-J.; Zhang, K.-Y.; Tu, S.-J.; Jiang, B. Org. Lett. 2018, 20, 3596.
6. [6]
  (a) Meadows, D. C.; Gervay-Hague, J. Med. Res. Rev. 2006, 26, 793; (b) Feng, M.; Tang, B.; Liang, S. H.; Jiang, X. Curr. Top. Med. Chem. 2016, 16, 1200; (c) Shaaban, S.; Liang, S.; Liu, N.-W.; Manolikakes, G. Org. Biomol. Chem. 2017, 15, 1947; (d) Qiu, G.; Zhou, K.; Gao, L.; Wu, J. Org. Chem. Front. 2018, 5, 691.
1. [1]
  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
2. [2]
  Xinyu Zhu , Meili Pang . Application of Functional Group Addition Strategy in Organic Synthesis. University Chemistry, 2024, 39(3): 218-230. doi: 10.3866/PKU.DXHX202308106
3. [3]
  Jinyao Du , Xingchao Zang , Ningning Xu , Yongjun Liu , Weisi Guo . Electrochemical Thiocyanation of 4-Bromoethylbenzene. University Chemistry, 2024, 39(6): 312-317. doi: 10.3866/PKU.DXHX202310039
4. [4]
  Tiantian MA , Sumei LI , Chengyu ZHANG , Lu XU , Yiyan BAI , Yunlong FU , Wenjuan JI , Haiying YANG . Methyl-functionalized Cd-based metal-organic framework for highly sensitive electrochemical sensing of dopamine. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 725-735. doi: 10.11862/CJIC.20230351
5. [5]
  Hongsheng Tang , Yonghe Zhang , Dexiang Wang , Xiaohui Ning , Tianlong Zhang , Yan Li , Hua Li . A Wonderful Journey through the Kingdom of Hazardous Chemicals. University Chemistry, 2024, 39(9): 196-202. doi: 10.12461/PKU.DXHX202403098
6. [6]
  Yufang GAO , Nan HOU , Yaning LIANG , Ning LI , Yanting ZHANG , Zelong LI , Xiaofeng LI . Nano-thin layer MCM-22 zeolite: Synthesis and catalytic properties of trimethylbenzene isomerization reaction. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1079-1087. doi: 10.11862/CJIC.20240036
7. [7]
  Fengqiao Bi , Jun Wang , Dongmei Yang . Specialized Experimental Design for Chemistry Majors in the Context of “Dual Carbon”: Taking the Assembly and Performance Evaluation of Zinc-Air Fuel Batteries as an Example. University Chemistry, 2024, 39(4): 198-205. doi: 10.3866/PKU.DXHX202311069
8. [8]
  Shiyan Cheng , Yonghong Ruan , Lei Gong , Yumei Lin . Research Advances in Friedel-Crafts Alkylation Reaction. University Chemistry, 2024, 39(10): 408-415. doi: 10.12461/PKU.DXHX202403024
9. [9]
  Wenyan Dan , Weijie Li , Xiaogang Wang . The Technical Analysis of Visual Software ShelXle for Refinement of Small Molecular Crystal Structure. University Chemistry, 2024, 39(3): 63-69. doi: 10.3866/PKU.DXHX202302060
10. [10]
  Yanxin Wang , Hongjuan Wang , Yuren Shi , Yunxia Yang . Application of Python for Visualizing in Structural Chemistry Teaching. University Chemistry, 2024, 39(3): 108-117. doi: 10.3866/PKU.DXHX202306005
11. [11]
  Yongming Guo , Jie Li , Chaoyong Liu . Green Improvement and Educational Design in the Synthesis and Characterization of Silver Nanoparticles. University Chemistry, 2024, 39(3): 258-265. doi: 10.3866/PKU.DXHX202309057
12. [12]
  Yingxian Wang , Tianye Su , Limiao Shen , Jinping Gao , Qinghe Wu . Introduction of Chinese Lacquer from the Perspective of Chemistry: Popularizing Chemistry in Lacquer and Inherit Lacquer Art. University Chemistry, 2024, 39(5): 371-379. doi: 10.3866/PKU.DXHX202312015
13. [13]
  Chengxia Tong , Yajie Li , Jin Yan , Xuejian Qu , Shigang Wei , Yong Fan , Zhiguang Song , Yupeng Guo . The Construction and Practice of a Comprehensive and Three-Dimensional Practical Education Model. University Chemistry, 2024, 39(7): 49-55. doi: 10.12461/PKU.DXHX202404155
14. [14]
  Xu Liu , Chengfang Liu , Jie Huang , Xiangchun Li , Wenyong Lai . Research on the Application of Diversified Teaching Models in the Teaching of Physical Chemistry. University Chemistry, 2024, 39(8): 112-118. doi: 10.3866/PKU.DXHX202402021
15. [15]
  Ruming Yuan , Laiying Zhang , Xiaoming Xu , Pingping Wu , Gang Fu . Application of Mathematica in Visualizing Physical Chemistry Formulas. University Chemistry, 2024, 39(8): 375-382. doi: 10.3866/PKU.DXHX202401030
16. [16]
  Dongxia Zhang , Sijia Hao , Jiarui Wang , Jiwei Wang , Xiaogang Dong , Liang Jiao . Construction and Reflection on the Safety Management of Hazardous Chemicals in University Laboratories. University Chemistry, 2024, 39(10): 229-235. doi: 10.12461/PKU.DXHX202403078
17. [17]
  Yunhao Zhang , Yinuo Wang , Siran Wang , Dazhen Xu . Progress in Selective Construction of Functional Aromatics from Nitrogenous Cycloalkanes. University Chemistry, 2024, 39(11): 136-145. doi: 10.3866/PKU.DXHX202401083
18. [18]
  Guangming YIN , Huaiyao WANG , Jianhua ZHENG , Xinyue DONG , Jian LI , Yi'nan SUN , Yiming GAO , Bingbing WANG . Preparation and photocatalytic degradation performance of Ag/protonated g-C₃N₄ nanorod materials. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1491-1500. doi: 10.11862/CJIC.20240086
19. [19]
  Yuqiao Zhou , Weidi Cao , Shunxi Dong , Lili Lin , Xiaohua Liu . Study on the Teaching Reformation of Practical X-ray Crystallography. University Chemistry, 2024, 39(3): 23-28. doi: 10.3866/PKU.DXHX202303003
20. [20]
  Hongyi Zhang , Zhihong Shi , Zhijun Zhang . A New Strategy for “De-formulized” Calculation of Dynamic Buffer Capacity in Analytical Chemistry Education. University Chemistry, 2024, 39(3): 390-394. doi: 10.3866/PKU.DXHX202309030

Get Citation

PDF

XML

Metrics

PDF Downloads(13)
Abstract views(1217)
HTML views(232)

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