Citation: Zhang Zhen, Gong Li, Zhou Xiao-Yu, Yan Si-Shun, Li Jing, Yu Da-Gang. Radical-Type Difunctionalization of Alkenes with CO₂[J]. Acta Chimica Sinica, ;2019, 77(9): 783-793. doi: 10.6023/A19060208 shu

Radical-Type Difunctionalization of Alkenes with CO₂

Zhang Zhen ^a,b ,
Gong Li ^b ,
Zhou Xiao-Yu ^b ,
Yan Si-Shun ^b ,
Li Jing ^b,, ,
Yu Da-Gang ^b,,

a.
Key Laboratory of Coarse Cereal Processing (Ministry of Agriculture and Rural Affairs), College of Pharmacy and Biological Engineering, Chengdu University, Chengdu 610106
b.
Key Laboratory of Green Chemistry & Technology of Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064

Corresponding author: Li Jing, jingli@scu.edu.cn Yu Da-Gang, dgyu@scu.edu.cn
Received Date: 12 June 2019
Available Online: 12 September 2019
Fund Project: the National Natural Science Foundation of China 21801025the National Natural Science Foundation of China 21822108the Fok Ying Tung Education Foundation 161013the "973" Project from the Ministry of Science and Technology of China 2015CB856600Project supported by the "973" Project from the Ministry of Science and Technology of China (No. 2015CB856600), the National Natural Science Foundation of China (Nos. 21822108, 21801025), the Fok Ying Tung Education Foundation (No. 161013) and the Fundamental Research Funds for the Central Universities

Figures(15)

CO₂ is an ideal C1 source in chemical transformations. It is of great significance to utilize CO₂ in chemical conversion to synthesize high value-added compounds, including carboxylic acids and carbonyl-containing heterocycles. On the other hand, the difunctionalization of olefins is an important organic reaction, which can efficiently convert easily available olefins into important compounds with structural diversity. However, due to the low reactivity of CO₂ and the difficulty in controlling the selectivity, the difunctionalization of olefins with CO₂ is highly challenging. Recently, the significant progress of radical chemistry has provided new strategies and promoted the development of novel transformations in this field. This Perspective summarizes the recent progress of the radical-type difunctionalization of olefins with CO₂, including the oxy-alkylation, carbocarboxylation, silacarboxylation, thiocarboxylation, and dicarboxylation of alkenes with CO₂. At the same time, we also highlight the mechanism with radicals and four kinds of pathways are proposed:(1) Free radicals attack olefins to form new carbon radical intermediates. The radicals are then oxidized to form carbocations, which are further captured by carbonates or carbamates. It is also possible for direct C-O bonding reaction or sequent C-I and C-O bonds formation. (2) The new carbon radical intermediates, in-situ generated through attack of alkenes with radicals, are reduced via single electron transfer into carbanions, which could attack CO₂to form C-C bonds. (3) CO₂is reduced into CO₂ radical anions in the highly reductive reaction conditions. Once generated, the CO₂ radical anions might attack olefins to form carboxylate bearing more stable carbon radical intermediates (such as benzylic ones) and further form C-C bonds or carbon-heteroatom bonds. (4) Olefins are reduced via single electron transfer into alkenyl free radical anions in the highly reductive reaction conditions. These anions may attack CO₂to form carboxylate bearing carbon radical intermediates and are further reduced to generate carbanions. Finally they may attack another CO₂to form succinic acid derivatives. We point out the challenges and predict the future development in the field, including the more challenging substrates, more reaction types, better selectivities, and deeper mechanistic understanding.
- carbon dioxide,
- olefin,
- difunctionalization,
- radical,
- visible-light photoredox catalysis
1. [1]
2. [2]
3. [3]
  (a) Sasano, K.; Takaya, J.; Iwasawa, N. J. Am. Chem. Soc. 2013, 135, 1251. (b) Sekine, K.; Sadamitsu, Y.; Yamada, T. Org. Lett. 2015, 17, 5706. (c) Moragas, T.; Gaydou, M.; Martin, R. Angew. Chem., Int. Ed. 2016, 55, 5053. (d) Miao, B.; Li, S.; Li, G.; Ma, S. Org. Lett. 2016, 18, 2556. (e) Nogi, K.; Fujihara, T.; Terao, J.; Tsuji, Y. J. Am. Chem. Soc. 2016, 138, 5547. (f) Gholap, S. S.; Takimoto, M.; Hou, Z. Chem. Eur. J. 2016, 22, 8547. (g) Yan, S.-S.; Zhu, L.; Ye, J.-H.; Zhang, Z.; Huang, H.; Zeng, H.; Li, C.-J.; Lan, Y.; Yu, D.-G. Chem. Sci. 2018, 9, 4873. (h) Song, L.; Zhu, L.; Zhang, Z.; Ye, J.-H.; Yan, S.-S.; Han, J.-L.; Yin, Z.-B.; Lan, Y.; Yu, D.-G. Org. Lett. 2018, 20, 3776. (i) Fu, L.; Li, S.; Cai, Z.; Ding, Y.; Guo, X.; Zhou, L.; Yuan, D.; Sun, Q.; Li, G. Nat. Catal. 2018, 1, 469. (j) Xiong, W. F.; Yan, D. H.; Qi, C. R.; Jiang, H. F. Org. Lett. 2018, 20, 672. (k) Wang, S.; Xi, C. J. Org. Lett. 2018, 20, 4131. (l) Song, L.; Cao, G.-M.; Zhou, W.; Ye, J.-H.; Zhang, Z.; Tian, X.-Y.; Li, J.; Yu, D.-G. Org. Chem. Front. 2018, 5, 2086. (m) Cai, Z.; Li, S.; Gao, Y.; Li, G. Adv. Synth. Catal. 2018, 360, 4005. (n) Huang, R.; Li, S.; Fu, L.; Li, G. Asian J. Org. Chem. 2018, 7, 1376. (o) Gao, Y.; Cai, Z.; Li, S.; Li, G. Org. Lett. 2019, 21, 3663. (p) Yan, S.-S.; Wu, D.-S.; Ye, J.-H.; Gong, L.; Zeng, X.; Ran, C.-K.; Gui, Y.-Y.; Li, J.; Yu, D.-G. ACS Catal. 2019, 9, 6987.
4. [4]
  (a) Seo, H; Katcher, M. H.; Jamison, T. F. Nat. Chem. 2017, 9, 453. (b) Meng, Q.; Wang, S.; König, B. Angew. Chem., Int. Ed. 2017, 56, 13426. (c) Shimomaki, K.; Murata, K.; Martin, R.; Iwasawa, N. J. Am. Chem. Soc. 2017, 139, 9467. (d) Liao, L.-L.; Cao, G.-M.; Ye, J.-H.; Sun, G.-Q.; Zhou, W.-J.; Gui, Y.-Y.; Yan, S.-S.; Shen, G.; Yu, D.-G. J. Am. Chem. Soc. 2018, 140, 17338. (e) Ju, T.; Fu, Q.; Ye, J.-H.; Zhang, Z.; Liao, L.-L.; Yan, S.-S.; Tian, X.-Y.; Luo, S.-P.; Li, J.; Yu, D.-G. Angew. Chem. Int. Ed. 2018, 57, 13897. (f) Fan, X.; Gong, X.; Ma, M.; Wang, R.; Walsh, P. J. Nat. Commun. 2018, 9, 4936.
5. [5]
  (a) Wang, H.; Lin, M.-Y.; Fang, H. J.; Chen, T. T.; Lu, J.-X. Chin. J. Chem. 2007, 25, 913. (b) Wang, H.; Du, Y. F.; Lin, M. Y.; Zhang, K.; Lu, J.-X. Chin. J. Chem. 2008, 26, 1745. (c) Jiao, K.; Li, Z.; Xu, X.; Zhang, L.; Li, Y.; Zhang, K.; Mei, T.-S. Org. Chem. Front. 2018, 5, 2244.
6. [6]
  (a) Xin, Z.; Lescot, C.; Friis, S. D.; Daasbjerg, Kim; Skrydstrup, T. Angew. Chem. Int. Ed. 2015, 54, 6862. (b) Zhang, W.; Yang, M. W.; Lv, X. Green Chem. 2016, 18, 4181. (c) Zhang, Z.; Liao, L.-L.; Yan, S.-S.; Wang, L.; He, Y.-Q.; Ye, J.-H.; Li, J.; Zhi, Y.-G.; Yu, D.-G. Angew. Chem., Int. Ed., 2016, 55, 7068. (d) Wang, S.; Shao, P.; Du, G.; Xi, C. J. Org. Chem. 2016, 81, 6672.
7. [7]
  (a) Hu, J.; Ma, J.; Zhu, Q.; Zhang, Z.; Wu, C.; Han, B. Angew. Chem. Int. Ed. 2015, 54, 5399. (b) Gao, X.; Yu, B.; Yang, Z.; Zhao, Y.; Zhang, H.; Hao, L.; Han, B.; Liu, Z. ACS Catal. 2015, 5, 6648. (c) Zhao, Y.; Wu, Y.; Yuan, G.; Hao, L.; Gao, X.; Yang, Z.; Yu, B.; Zhang, H.; Liu, Z. Chem. Asian J. 2016, 11, 2735.
8. [8]
  (a) Li, Y.; Fang, X.; Junge, K.; Beller, M. Angew. Chem. Int. Ed. 2013, 52, 9568. (b) Zhang, Z.; Sun, Q.; Xia, C.; Sun, W. Org. Lett. 2016, 18, 6316. (c) Zhang, Y.; Wang, H.; Yuan, H.; Shi, F. ACS Sustainable Chem. Eng. 2017, 5, 5758. (d) Ren, X.; Zheng, Z.; Zhang, L.; Wang, Z.; Xia, C.; Ding, K. Angew. Chem., Int. Ed. 2017, 56, 310.
9. [9]
  (a) Lehn, J.-M.; Ziessel, R. Proc. Natl. Acad. Sci. USA 1982, 79, 701. (b) Burgess, S. A.; Kendall, A. J.; Tyler, D. R.; Linehan, J. C.; Appel, A. M. ACS Catal. 2017, 7, 3089.
10. [10]
  (a) Pupo, G.; Properzi, R.; List, B. Angew. Chem., Int. Ed. 2016, 55, 6099. (b) Riemer, D.; Mandaviya, B.; Schilling, W.; Götz, A. C.; Kühl, T.; Finger, M.; Das, S. ACS Catal. 2018, 8, 3030. (c) Roy, T.; Kim, M. J.; Yang, Y.; Kim, S.; Kang, G.; Ren, X.; Kadziola, A.; Lee, H.-Y.; Baik, M.-H. Lee, J.-W. ACS Catal. 2019, 9, 6006.
11. [11]
  For selected reviews, see: (a) Cao, M.-Y.; Ren, X.; Lu, Z. Tetrahedron Lett. 2015, 56, 3732. (b) Chen, J.-R.; Yu, X.-Y.; Xiao, W.-J. Synthesis 2015, 47, 604. (c) Koike, T.; Akita, M. Acc. Chem. Res. 2016, 49, 1937. (d) Koike, T.; Akita, M. Chem 2018, 4, 409. (e) Li, W.; Xu, W.; Xie, J.; Yu, S.; Zhu, C. Chem. Soc. Rev. 2018, 47, 654. (f) Wu, X.; Wu, S.; Zhu, C. Tetrahedron Lett. 2018, 59, 1328.
12. [12]
  (a) Yan, M.; Kawamata, Y.; Baran, P. S. Chem. Rev. 2017, 117, 13230. (b) Zhang, Z.; Ye, J.-H.; Wu, D.-S.; Zhou, Y.-Q.; Yu, D.-G. Chem. Asian J. 2018, 13, 2292. (c) Peshkov, V. A.; Pereshivko, O. P.; Nechaev, A. A; Peshkov, A. A.; Vander Eycken, E. V. Chem. Soc. Rev. 2018, 47, 3861. (d) Tortajada, A.; Juliá-Hernández, F.; Börjesson, M.; Moragas, T.; Martin, R. Angew. Chem., Int. Ed. 2018, 57, 15948. (e) Yan, S.-S.; Fu, Q.; Liao, L.-L.; Sun, G.-Q.; Ye, J.-H.; Gong, L.; Bo-Xue, Y.-Z.; Yu, D.-G. Coord. Chem. Rev. 2018, 374, 439. (f) Cao, Y.; He, X.; Wang, N.; Li, H.-R.; He, L.-N. Chin. J. Chem. 2018, 36, 644. (g) Hou, J.; Li, J.-S.; Wu, J. Asian J. Org. Chem. 2018, 7, 1439. (h) Tan, F.; Yin, G. Chin. J. Chem. 2018, 36, 545. (i) Yeung, C. S. Angew. Chem., Int. Ed. 2019, 58, 5492.
13. [13]
  Luan, Y.-X.; Ye, M. Tetrahedron Lett. 2018, 59, 853. doi: 10.1016/j.tetlet.2018.01.035
14. [14]
  (a) Tominaga, K.-I.; Sasaki, Y. Catal. Commun. 2000, 1, 1. (b) Tominaga, K.-i.; Sasaki, Y. J. Mol. Catal. A: Chem. 2004, 220, 159. (c) Liu, Q.; Wu, L.; Fleischer, I.; Selent, D.; Franke, R.; Jackstell, R.; Beller, M. Chem.-Eur. J. 2014, 20, 6888. (d) Tani, Y.; Kuga, K.; Fujihara, T.; Terao, J.; Tsuji, Y. Chem. Commun. 2015, 51, 13020. (e) Gui, Y.-Y.; Hu, N.; Chen, X.-W.; Liao, L.-L.; Ju, T.; Ye, J.-H.; Zhang, Z.; Li, J.; Yu, D.-G. J. Am. Chem. Soc. 2017, 139, 17011.
15. [15]
  Seo, H.; Liu, A.-F.; Jamison, T. F. J. Am. Chem. Soc. 2017, 139, 13969. doi: 10.1021/jacs.7b05942
16. [16]
  (a) Evans, D. A.; Bartroli, J.; Shih, L. T. J. Am. Chem. Soc. 1981, 103, 2127. (b) Pandit, N.; Singla, R. K.; Shrivastava, B. Int. J. Med. Chem. 2012, 2012, 159285. (c) Ed.: Acton, Q. A., Oxazolidinones-Advances in Research and Application, Scholarly Editions, Atlanta, U.S., 2012.
17. [17]
  Ye, J.-H.; Song, L.; Zhou, W.-J.; Ju, T.; Yin, Z.-B.; Yan, S.-S.; Zhang, Z.; Li, J.; Yu, D.-G. Angew. Chem. Int. Ed. 2016, 55, 10022. doi: 10.1002/anie.201603352
18. [18]
  Zhu, L.; Ye, J.-H.; Duan, M.; Qi, X.; Yu, D.-G.; Bai, R.; Lan, Y. Org. Chem. Front. 2018, 5, 633. doi: 10.1039/C7QO00838D
19. [19]
  Ye, J.-H.; Zhu, L.; Yan, S.-S.; Miao, M.; Zhang, X.-C.; Zhou, W.-J.; Li, J.; Lan, Y.; Yu, D.-G. ACS Catal. 2017, 7, 8324. doi: 10.1021/acscatal.7b02533
20. [20]
  Wang, M.-Y.; Cao, Y.; Liu, X.; Wang, N.; He, L.-N.; Li, S.-H. Green Chem. 2017, 19, 1240. doi: 10.1039/C6GC03200A
21. [21]
  Yin, Z.-B.; Ye, J.-H.; Zhou, W.-J.; Zhang, Y.-H.; Ding, L.; Gui, Y.-Y.; Yan, S.-S.; Li, J.; Yu, D.-G. Org. Lett. 2017, 20, 190.
22. [22]
  Zhou, W.-J.; Cao, G.-M.; Sen, G.; Zhu, X.-Y.; Gui, Y.-Y.; Ye, J.-H.; Sun, L.; Liao, L.-L.; Li, J.; Yu, D.-G. Angew. Chem., Int. Ed. 2017, 56, 15683. doi: 10.1002/anie.201704513
23. [23]
  (a) Sun, L.; Ye, J.-H.; Zhou, W.-J.; Zeng, X.; Yu, D.-G. Org. Lett. 2018, 20, 3049. (b) For a very recent work, see: Sun, S.; Zhou, C.; Yu, J.-T.; Cheng, J. Org. Lett. 2019, DOI: 10.1021/acs.org-lett.9b02700.
24. [24]
  Yatham, V. R.; Shen, Y.; Martin, R. Angew. Chem., Int. Ed. 2017, 56, 10915. doi: 10.1002/anie.201706263
25. [25]
  Hou, J.; Ee, A.; Cao, H.; Ong, H.-W.; Xu, J.-H.; Wu J. Angew. Chem., Int. Ed. 2017, 57, 17220.
26. [26]
  Ye, J.-H.; Miao, M.; Huang, H.; Yan, S.-S.; Yin, Z.-B.; Zhou, W.-J.; Yu, D.-G. Angew. Chem., Int. Ed. 2017, 56, 15416. doi: 10.1002/anie.201707862
27. [27]
  Senboku, H.; Komatsu, H.; Fujimura, Y.; Tokuda, M. Synlett 2001, 2001, 418. doi: 10.1055/s-2001-11417
28. [28]
  Yuan, G.-Q.; Jiang, H.-F.; Lin, C.; Liao, S.-J. Electrochim. Acta 2008, 53, 2170. doi: 10.1016/j.electacta.2007.09.023
29. [29]
  Li, C.-H.; Yuan, G.-Q.; Ji, X.-C.; Wang, X.-J.; Ye, J.-S.; Jiang, H.-F. Electrochim. Acta 2011, 56, 1529. doi: 10.1016/j.electacta.2010.06.057
30. [30]
  For a very recent work on phosphonocarboxylation of alkenes with CO₂, see: Fu, Q.; Bo, Z.-Y.; Ye, J.-H.; Ju, T.; Huang, H.; Liao, L.-L.; Yu, D.-G. Nat. Commun. 2019, 10, 3592.
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]
  Yurong Tang , Yunren Shi , Yi Xu , Bo Qin , Yanqin Xu , Yunfei Cai . Innovative Experiment and Course Transformation Practice of Visible-Light-Mediated Photocatalytic Synthesis of Isoquinolinone. University Chemistry, 2024, 39(5): 296-306. doi: 10.3866/PKU.DXHX202311087
3. [3]
  Lei Shi . Nucleophilicity and Electrophilicity of Radicals. University Chemistry, 2024, 39(11): 131-135. doi: 10.3866/PKU.DXHX202402018
4. [4]
  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
5. [5]
  Zhiquan Zhang , Baker Rhimi , Zheyang Liu , Min Zhou , Guowei Deng , Wei Wei , Liang Mao , Huaming Li , Zhifeng Jiang . Insights into the Development of Copper-based Photocatalysts for CO₂ Conversion. Acta Physico-Chimica Sinica, 2024, 40(12): 2406029-. doi: 10.3866/PKU.WHXB202406029
6. [6]
  Jie ZHAO , Huili ZHANG , Xiaoqing LU , Zhaojie WANG . Theoretical calculations of CO₂ capture and separation by functional groups modified 2D covalent organic framework. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 275-283. doi: 10.11862/CJIC.20240213
7. [7]
  Weihan Zhang , Menglu Wang , Ankang Jia , Wei Deng , Shuxing Bai . 表面硫物种对钯-硫纳米片加氢性能的影响. Acta Physico-Chimica Sinica, 2024, 40(11): 2309043-. doi: 10.3866/PKU.WHXB202309043
8. [8]
  Yueguang Chen , Wenqiang Sun . “Carbon” Adventures. University Chemistry, 2024, 39(9): 248-253. doi: 10.3866/PKU.DXHX202308074
9. [9]
  Bing WEI , Jianfan ZHANG , Zhe CHEN . Research progress in fine tuning of bimetallic nanocatalysts for electrocatalytic carbon dioxide reduction. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 425-439. doi: 10.11862/CJIC.20240201
10. [10]
  Bo YANG , Gongxuan LÜ , Jiantai MA . Nickel phosphide modified phosphorus doped gallium oxide for visible light photocatalytic water splitting to hydrogen. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 736-750. doi: 10.11862/CJIC.20230346
11. [11]
  Wei HE , Jing XI , Tianpei HE , Na CHEN , Quan YUAN . Application of solar-driven inorganic semiconductor-microbe hybrids in carbon dioxide fixation and biomanufacturing. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 35-44. doi: 10.11862/CJIC.20240364
12. [12]
  .
  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): -.
13. [13]
  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
14. [14]
  Xinzhe HUANG , Lihui XU , Yue YANG , Liming WANG , Zhangyong LIU , Zhongjian WANG . Preparation and visible light responsive photocatalytic properties of BiSbO₄/BiOBr. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 284-292. doi: 10.11862/CJIC.20240212
15. [15]
  Qin Li , Huihui Zhang , Huajun Gu , Yuanyuan Cui , Ruihua Gao , Wei-Lin Dai . In situ Growth of Cd_0.5Zn_0.5S Nanorods on Ti₃C₂ MXene Nanosheet for Efficient Visible-Light-Driven Photocatalytic Hydrogen Evolution. Acta Physico-Chimica Sinica, 2025, 41(4): 100031-. doi: 10.3866/PKU.WHXB202402016
16. [16]
  Bing LIU , Huang ZHANG , Hongliang HAN , Changwen HU , Yinglei ZHANG . Visible light degradation of methylene blue from water by triangle Au@TiO₂ mesoporous catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 941-952. doi: 10.11862/CJIC.20230398
17. [17]
  Jie Li , Huida Qian , Deyang Pan , Wenjing Wang , Daliang Zhu , Zhongxue Fang . Efficient Synthesis of Anethaldehyde Induced by Visible Light. University Chemistry, 2024, 39(4): 343-350. doi: 10.3866/PKU.DXHX202310076
18. [18]
  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
19. [19]
  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
20. [20]
  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

Get Citation

PDF

XML

Metrics

PDF Downloads(126)
Abstract views(4325)
HTML views(1324)

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

Radical-Type Difunctionalization of Alkenes with CO2

Metrics

通讯作者: 陈斌, bchen63@163.com

Radical-Type Difunctionalization of Alkenes with CO₂