Citation: Lu Fu-Dong, Jiang Xuan, Lu Liang-Qiu, Xiao Wen-Jing. Application of Propargylic Radicals in Organic Synthesis[J]. Acta Chimica Sinica, ;2019, 77(9): 803-813. doi: 10.6023/A19060201 shu

Application of Propargylic Radicals in Organic Synthesis

Lu Fu-Dong ^a ,
Jiang Xuan ^a ,
Lu Liang-Qiu ^a,, ,
Xiao Wen-Jing ^a,b,,

a.
Key Laboratory of Pesticide & Chemical Biology Ministry of Education and College of Chemistry, Central China Normal University, Wuhan 430079
b.
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032

Corresponding author: Lu Liang-Qiu, luliangqiu@mail.ccnu.edu.cn Xiao Wen-Jing, wxiao@mail.ccnu.edu.cn
Received Date: 8 June 2019
Available Online: 13 September 2019
Fund Project: the National Natural Science Foundation of China 21772053the Natural Science Foundation of Hubei Province 2017AHB047the Natural Science Foundation of Hubei Province 2015CFA033the National Natural Science Foundation of China 21772052Project supported by the National Natural Science Foundation of China (Nos. 21572074, 21772052 and 21772053) and the Natural Science Foundation of Hubei Province (Nos. 2015CFA033, 2017AHB047)the National Natural Science Foundation of China 21572074

Figures(20)

The production and transformation of alkynes occupys an important position in organic synthetic chemistry. Within this realm, propargylic functionalization of alkynes is a feasible way towards this purpose. Especially, the propargylic functionalization via radical pathways has flourished in the last decade, which is believed to be a significant complement to the classic metal-catalyzed propargylation reaction involving cationic intermediates. According to the reaction modes, these advancements will be highlighted by classifying into four types. The first one is the propargylic functionalization reactions involving propargylic radicals. Generally, propargylic radicals can be generated through single electron reduction of alkyne substrates by low-valence metal catalysts or excited state of photocatalysts, then participated in the following cross-coupling reactions to achieve alkyne products. In this part, asymmetric variants have been also well developed. The second one is the preparation of allene compounds through the allenyl radical pathway. For these processes, propargylic radicals can isomerize to allenyl radicals, which can participate in the copper-or nickel-catalyzed coupling reaction to produce significant allene compounds. The third one is the dehydrative alkylation reaction of propargyl alcohols that involve propargylic radical intermediates, too. Such radical intermediates can be further oxidized to propargylic cation intermediates, followed by a deprotonation to form substituted 1, 3-enyne compounds. The forth one is the synthesis of vinylic alkoxyamines through a propargylic radical route. Initially, propargyl alcohols can be converted to propargylic radical species by the joint action of copper catalysts and TEMPO. The generated propargylic radical species can be captured by TEMPO to form vinylic alkoxyamines. Finally, an outlook on the radical propargylic functionalizations will be provided at the end of this review.
- propargylic radical,
- propargylic functionalization,
- alkyne,
- allene,
- transition metal catalysis
1. [1]
  (a) Trost, B. M.; Li, C.-J. Modern Alkyne Chemistry: Catalytic and Atom-Economic Transformations, Wiley-VCH, New York, 2014. (b) Trotuş, I. T.; Zimmermann, T.; Schüth, F. Chem. Rev. 2014, 114, 1761. (c) Tiwari, V. K.; Mishra, B. B.; Mishra, K. B.; Mishra, N.; Singh, A. S.; Chen, X. Chem. Rev. 2016, 116, 3086. (d) Huang, D.; Liu, Y.; Qin, A.-J.; Tang, B.-Z. Polym. Chem. 2018, 9, 2853.
2. [2]
  Ding, C.-H.; Hou, X.-L. Chem. Rev. 2011, 111, 1914. doi: 10.1021/cr100284m
3. [3]
  (a) Nicholas, K. M.; Pettit, R. Tetrahedron Lett. 1971, 37, 3475. (b) Nicholas, K. M.; Pettit, R. J. Organomet. Chem. 1972, 44, 21.
4. [4]
  Melikyan, G. G. Acc. Chem. Res. 2015, 48, 1065. doi: 10.1021/ar500365v
5. [5]
  Geri, R.; Oilizzi, C.; Lardicci, L.; Caporusso, A. M. Gazz. Chim. Ital. 1994, 124, 241.
6. [6]
7. [7]
  Bruneau, C.; Dixneuf, P. H. Metal Vinylidenes and Allenylidenes in Catalysis, Wiley-VCH, Weinheim, 2008.
8. [8]
  (a) Kropf, H.; SchrÖder, R.; FÖlsing, R. Synthesis 1977, 894. (b) Alvarez, L. X.; Christ, M. L.; Sorokin, A. B. Appl. Catal. A: Gen. 2007, 325, 303.
9. [9]
  Smith, S. W.; Fu, G. C. J. Am. Chem. Soc. 2008, 130, 12645. doi: 10.1021/ja805165y
10. [10]
  Oelke, A. J.; Sun, J.-W.; Fu, G. C. J. Am. Chem. Soc. 2012, 134, 2966. doi: 10.1021/ja300031w
11. [11]
  Pelphrey, P. M.; Popov, V. M.; Joska, T. M.; Beierlein, J. M.; Bolstad, E. S. D.; Fillingham, Y. A.; Wright, D. L.; Anderson, A. C. J. Med. Chem. 2007, 50, 940. doi: 10.1021/jm061027h
12. [12]
  Schley, N. D.; Fu, G. C. J. Am. Chem. Soc. 2014, 136, 16588. doi: 10.1021/ja508718m
13. [13]
  Domingo-Legarda, P.; Soler-Yanes, R.; Quirós-López, M. T.; Buñuel, E.; Cárdenas, D. J. Eur. J. Org. Chem. 2018, 35, 4900.
14. [14]
  An, L.; Tong, F.-F.; Zhang, X.-G. Acta Chim. Sinica 2018, 76, 977(in Chinese).
15. [15]
  Lu, F.-D.; Liu, D.; Zhu, L.; Lu, L.-Q.; Yang, Q.; Zhou, Q.-Q.; Wei, Y.; Lan, Y.; Xiao, W.-J. J. Am. Chem. Soc. 2019, 141, 6167. doi: 10.1021/jacs.9b02338
16. [16]
  Cheng, J.-K.; Loh, T.-P. J. Am. Chem. Soc. 2015, 137, 42. doi: 10.1021/ja510635k
17. [17]
  Andia, A. A.; Miner, M. R.; Woerpel, K. A. Org. Lett. 2015, 17, 2704. doi: 10.1021/acs.orglett.5b01120
18. [18]
  Miner, M. R.; Woerpel, K. A. Eur. J. Org. Chem. 2016, 1860.
19. [19]
  Cheng, J.-K.; Shen, L.; Wu, L.-H.; Hu, X.-H.; Loh, T.-P. Chem. Commun. 2017, 53, 12830. doi: 10.1039/C7CC08074C
20. [20]
21. [21]
  (a) Wartenberg, F.-H.; Junga, H.; Blechert, S. Tetrahedron Lett. 1993, 34, 5251. (b) Alameda-Angulo, C.; Quiclet-Sire, B.; Zard, S. Z. Tetrahedron Lett. 2006, 47, 913.
22. [22]
  Soler-Yanes, R.; Arribas-Álvarez, I.; Guisán-Ceinos, M.; Buñuel, E.; Cárdenas, D. J. Chem. Eur. J. 2017, 23, 1584. doi: 10.1002/chem.201603758
23. [23]
  Wang, F.; Wang, D.-H.; Zhou, Y.; Liang, L.; Lu, R.-H.; Chen, P.-H.; Lin, Z.-Y.; Liu, G.-S. Angew. Chem., Int. Ed. 2018, 57, 7140. doi: 10.1002/anie.201803668
24. [24]
  Zhu, X.; Deng, W.; Chiou, M.-F.; Ye, C.; Jian, W.; Zeng, Y.; Jiao, Y.; Ge, L.; Li, Y.; Zhang, X.; Bao, H. J. Am. Chem. Soc. 2019, 141, 548. doi: 10.1021/jacs.8b11499
25. [25]
  Ye, C.-Q.; Li, Y.-J.; Zhu, X.-T.; Hu, S.-M.; Yuan, D.-Q.; Bao, H.-L. Chem. Sci. 2019, 10, 3632. doi: 10.1039/C8SC05689G
26. [26]
  Zhang, K.-F.; Bian, K.-J.; Li, C.; Sheng, J.; Li, Y.; Wang, X.-S. Angew. Chem. Int. Ed. 2019, 58, 5069. doi: 10.1002/anie.201813184
27. [27]
  Ye, C.-Q.; Qian, B.; Li, Y.-J.; Su, M.; Li, D.-L.; Bao, H.-L. Org. Lett. 2018, 20, 3202. doi: 10.1021/acs.orglett.8b01043
28. [28]
  Kang, Y.-W.; Choi, Y.-J.; Jang, H.-Y. Org. Lett. 2014, 16, 4842. doi: 10.1021/ol502341f
29. [29]
  Horn, E. J.; Rosen, B. R.; Chen, Y.; Tang, J.; Chen, K.; Eastgate, M. D.; Baran, P. S. Nature 2016, 533, 77. doi: 10.1038/nature17431
1. [1]
  Geyang Song , Dong Xue , Gang Li . Recent Advances in Transition Metal-Catalyzed Synthesis of Anilines from Aryl Halides. University Chemistry, 2024, 39(2): 321-329. doi: 10.3866/PKU.DXHX202308030
2. [2]
  Yan Li , Xinze Wang , Xue Yao , Shouyun Yu . Kinetic Resolution Enabled by Photoexcited Chiral Copper Complex-Mediated Alkene E→Z Isomerization: A Comprehensive Chemistry Experiment for Undergraduate Students. University Chemistry, 2024, 39(5): 1-10. doi: 10.3866/PKU.DXHX202309053
3. [3]
  Zhengyu Zhou , Huiqin Yao , Youlin Wu , Teng Li , Noritatsu Tsubaki , Zhiliang Jin . Synergistic Effect of Cu-Graphdiyne/Transition Bimetallic Tungstate Formed S-Scheme Heterojunction for Enhanced Photocatalytic Hydrogen Evolution. Acta Physico-Chimica Sinica, 2024, 40(10): 2312010-. doi: 10.3866/PKU.WHXB202312010
4. [4]
  Jie ZHAO , Sen LIU , Qikang YIN , Xiaoqing LU , Zhaojie WANG . Theoretical calculation of selective adsorption and separation of CO₂ by alkali metal modified naphthalene/naphthalenediyne. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 515-522. doi: 10.11862/CJIC.20230385
5. [5]
  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
6. [6]
  Lei Shi . Nucleophilicity and Electrophilicity of Radicals. University Chemistry, 2024, 39(11): 131-135. doi: 10.3866/PKU.DXHX202402018
7. [7]
  Yue Zhao , Yanfei Li , Tao Xiong . Copper Hydride-Catalyzed Nucleophilic Additions of Unsaturated Hydrocarbons to Aldehydes and Ketones. University Chemistry, 2024, 39(4): 280-285. doi: 10.3866/PKU.DXHX202309001
8. [8]
  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
9. [9]
  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
10. [10]
  Tingbo Wang , Yao Luo , Bingyan Hu , Ruiyuan Liu , Jing Miao , Huizhe Lu . Quantitative Computational Study on the Claisen Rearrangement Reaction of Allyl Phenyl Ethers: An Introduction to a Computational Chemistry Experiment. University Chemistry, 2024, 39(11): 278-285. doi: 10.12461/PKU.DXHX202403082
11. [11]
  Zhuo WANG , Junshan ZHANG , Shaoyan YANG , Lingyan ZHOU , Yedi LI , Yuanpei LAN . Preparation and photocatalytic performance of CeO₂-reduced graphene oxide by thermal decomposition. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1708-1718. doi: 10.11862/CJIC.20240067
12. [12]
  Fei Xie , Chengcheng Yuan , Haiyan Tan , Alireza Z. Moshfegh , Bicheng Zhu , Jiaguo Yu . d带中心调控过渡金属单原子负载COF吸附O₂的理论计算研究. Acta Physico-Chimica Sinica, 2024, 40(11): 2407013-. doi: 10.3866/PKU.WHXB202407013
13. [13]
  Yan LIU , Jiaxin GUO , Song YANG , Shixian XU , Yanyan YANG , Zhongliang YU , Xiaogang HAO . Exclusionary recovery of phosphate anions with low concentration from wastewater using a CoNi-layered double hydroxide/graphene electronically controlled separation film. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1775-1783. doi: 10.11862/CJIC.20240043
14. [14]
  Xiaofeng Zhu , Bingbing Xiao , Jiaxin Su , Shuai Wang , Qingran Zhang , Jun Wang . Transition Metal Oxides/Chalcogenides for Electrochemical Oxygen Reduction into Hydrogen Peroxides. Acta Physico-Chimica Sinica, 2024, 40(12): 2407005-. doi: 10.3866/PKU.WHXB202407005
15. [15]
  Yongpo Zhang , Xinfeng Li , Yafei Song , Mengyao Sun , Congcong Yin , Chunyan Gao , Jinzhong Zhao . Synthesis of Chlorine-Bridged Binuclear Cu(I) Complexes Based on Conjugation-Driven Cu(II) Oxidized Secondary Amines. University Chemistry, 2024, 39(5): 44-51. doi: 10.3866/PKU.DXHX202309092
16. [16]
  Guimin ZHANG , Wenjuan MA , Wenqiang DING , Zhengyi FU . Synthesis and catalytic properties of hollow AgPd bimetallic nanospheres. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 963-971. doi: 10.11862/CJIC.20230293
17. [17]
  Wenxiu Yang , Jinfeng Zhang , Quanlong Xu , Yun Yang , Lijie Zhang . Bimetallic AuCu Alloy Decorated Covalent Organic Frameworks for Efficient Photocatalytic Hydrogen Production. Acta Physico-Chimica Sinica, 2024, 40(10): 2312014-. doi: 10.3866/PKU.WHXB202312014
18. [18]
  Ping ZHANG , Chenchen ZHAO , Xiaoyun CUI , Bing XIE , Yihan LIU , Haiyu LIN , Jiale ZHANG , Yu'nan CHEN . Preparation and adsorption-photocatalytic performance of ZnAl@layered double oxides. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1965-1974. doi: 10.11862/CJIC.20240014
19. [19]
  Guojie Xu , Fang Yu , Yunxia Wang , Meng Sun . Introduction to Metal-Catalyzed β-Carbon Elimination Reaction of Cyclopropenones. University Chemistry, 2024, 39(8): 169-173. doi: 10.3866/PKU.DXHX202401060
20. [20]
  Lu XU , Chengyu ZHANG , Wenjuan JI , Haiying YANG , Yunlong FU . Zinc metal-organic framework with high-density free carboxyl oxygen functionalized pore walls for targeted electrochemical sensing of paracetamol. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 907-918. doi: 10.11862/CJIC.20230431

Get Citation

PDF

XML

Metrics

PDF Downloads(75)
Abstract views(3595)
HTML views(1159)

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