Citation: Zhou Quanquan, Liu Dan, Xiao Wenjing, Lu Liangqiu. Visible-Light Photoredox Catalytic α-Cyanation Reactions of Tertiary Amines[J]. Acta Chimica Sinica, ;2017, 75(1): 110-114. doi: 10.6023/A16080414 shu

Visible-Light Photoredox Catalytic α-Cyanation Reactions of Tertiary Amines

Key Laboratory of Pesticide & Chemical Biology Ministry of Education and College of Chemistry, Central China Normal University, Wuhan 430079

Corresponding author: Lu Liangqiu, luliangqiu@mail.ccnu.edu.cn
Received Date: 15 August 2016

Fund Project: National Natural Science Foundation of China 21232003National Natural Science Foundation of China 21572074National Natural Science Foundation of China 21472057

Figures(5)

Visible-light photoredox catalysis, a novel and green catalytic strategy, has recently received increasing attention from chemists and been widely applied to organic synthesis in the past years. This catalytic strategy enables the generation of various reactive species under mild conditions without stoichiometric activation reagents and shows its significance for sustainable chemistry. α-Amino nitriles are highly versatile intermediates having extensive applications in organic synthesis and biological transformation. The oxidation of tertiary amines using stoichiometric oxidants followed by the nucleophilic addition reaction of the iminium intermediate by cyanide ion (CN^-) represents a direct approach for their synthesis. However, the use of stoichiometric oxidants and the production of huge amounts of hazardous waste (i.e., CN^-) is undesirable from environmental viewpoints. Here, we report a photoredox catalytic α-cyanation reaction of tertiary amines using cyanobenziodoxol as a stable and safe cyanide source. This protocol is favored for mild conditions, the avoidance of extra oxidant and highly toxic cyano anion, good functional tolerance as well as safe and simple operations. By doing so, a variety of α-amino nitriles are afforded in good to excellent yields. A sunlight-driven reaction and a gram-scale reaction further demonstrate the utility of this methodology. In addition, we also succeed to apply the same strategy to the decarboxylative cyanation of carboxylic acids, affording the nitriles in moderate yields. A possible mechanism was proposed on the basis of known literature and our previous reports. The representative procedure for the α-cyanation reaction of tertiary amines is as following:N-phenyl piperidine 1a (0.48 mmol), cyanobenziodoxol 2a (0.40 mmol), photocatalyst Ir[dF (CF₃) PPy]₂(dtbbpy) PF₆ (0.008 mmol) and CsHCO₃ (0.60 mmol) were dissolved in DCM (8 mL). Then, the resulting mixture was degassed via 'freeze-pump-thaw' procedure (3 times). After that, the solution was stirred at a distance of ca. 5 cm from a 7 W blue LEDs (450~460 nm) at room temperature for 16 h. Upon completion, the crude product was purified by flash chromatography on silica gel (petroleum ether/ethyl acetate 30:1~10:1) directly to give the desired product. The procedure for the decarboxylative cyanation of carboxylic acids is similar.
- visible-light photoredox catalysis,
- cyanation,
- α-amino nitrile,
- tertiary amine,
- decarboxylative transformation
1. [1]
  (a) Enders, D.; Shilvock, J. P. Chem. Soc. Rev. 2000, 29, 359; (b) Martinez, E. J.; Corey, E. J. Org. Lett. 1999, 1, 75; (c) Dyker, G. Angew. Chem., Int. Ed. 1997, 36, 1700; (d) North, M. Angew. Chem. Int. Ed. 2004, 43, 4126; (e) En, D.; Zou, G.-F.; Guo, Y.; Liao, W.-W. J. Org. Chem. 2014, 79, 4456; (f) Qin, T.-Y.; Zhang, X.-A.; Liao, W.-W. Chin. J. Org. Chem. 2014, 34, 2187. (秦天游, 张晓安, 寮渭巍, 有机化学, 2014, 34, 2187).
2. [2]
  (a) Ishitani, H.; Komiyama, S.; Kobayashi, S. Angew. Chem., Int. Ed. 1998, 3186; (b) Surendra, K.; Krishnaveni, N. S.; Mahesh, A.; Rao, K. R. J. Org. Chem. 2006, 2532; (c) Wang, J.; Liu, X.; Feng, X. Chem. Rev. 2011, 111, 6947.
3. [3]
  Selected examples, see: (a) Han, W.; Ofial, A. R. Chem. Commun.2009, 33, 5024; (b) Boess, E.; Schmitz, C.; Klussmann, M. J. Am. Chem. Soc. 2012, 134, 5317; (c) Murahashi, S.; Komiya, N.; Terai, H.; Nakae, T. J. Am. Chem. Soc. 2003, 125, 15312; (d) Zhang, Y.; Peng, H.; Zhang, M.; Cheng, Y.; Zhu, C. Chem. Commun. 2011, 2354; (e) Alagiri, K.; Prabhu, K. R. Org. Biomol. Chem. 2012, 10, 835; (f) Lin, A.; Peng, H.; Abdukader, A.; Zhu, C. Eur. J. Org. Chem. 2013, 32, 7286; (g) Inghal, S.; Jain, S. L.; Sain, B. Chem. Commun. 2009, 2371; (h) Sakai, N.; Mutsuro, A.; Ikeda, R.; Konakahara, T. Synlett 2013, 1283; (i) Zhao, P.; Yin, Y.-W. Chin. J. Org. Chem.2004, 24, 916. (赵萍, 尹应武, 有机化学, 2004, 24, 916).
4. [4]
  For selected reviews on the visible light photocatalysis, see: (a) Narayanam, J. M.; Stephenson, C. R. Chem. Soc. Rev. 2011, 40; (b) Shi, L.; Xia, W. Chem. Soc. Rev. 2012, 41, 7687; (c) Xuan, J.; Xiao, W. J. Angew. Chem., Int. Ed. 2012, 51, 6828; (d) Prier, C. K.; Rankic, D. A.; MacMillan, D. W. C. Chem. Rev. 2013, 113, 5322; (e) Schultz, D. M.; Yoon, T. P. Science 2014, 343, 1239176; (f) Shaw, M. H.; Twilton, J.; MacMillan, D.W. C. J. Org. Chem. 2016, 81, 6898; (g) Karkas, M. D.; Porco, Jr J. A.; Stephenson, C. R. Chem. Rev. 2016, 116, 9683; (h) Romero, N. A.; Nicewicz, D. A. Chem. Rev. 2016, 116, 10075.
5. [5]
  For recent examples on the visible light-induced cyanation reactions, see: (a) Rueping, M.; Zhu, S.; Koenigs, R. M. Chem. Commun. 2011, 47, 12709; (b) Freeman, D. B.; Furst, L.; Condie, A. G.; Stephenson, C. R. J. Org. Lett. 2012, 14, 94; (c) Franz, J. F.; Kraus, W. B.; Zeitler, K. Chem. Commun. 2015, 51, 8280; (d) Hari, D. P.; Konig, B. Org. Lett. 2011, 13, 3852; (e) Pacheco, O. J. C.; Lipp, A.; Nauth, A. M.; Acke, F.; Dietz, J. P.; Opatz, T. Chem. Eur. J. 2016, 22, 5409.
6. [6]
  (a) Zhdankin, V. V.; Stang, P. J. Chem. Rev. 2008, 108, 5299; (b) Zhdankin, V. V. Hypervalent Iodine Chemistry: Preparation, Structure, and Synthetic Applications of Polyvalent Iodine Compounds, Wiley, Chichester, 2013; (c) Li, Y.-F.; Hari, D.-P.; Vita, M. V.; Waser, J. Angew. Chem., Int. Ed. 2016, 55, 4436.
7. [7]
  For recent works on visible light photocatalysis from our group, see: (a) Xuan, J.; Xia, X.-D.; Zeng, T.-T.; Feng, Z.-J.; Chen, J.-R.; Lu, L.-Q.; Xiao, W.-J. Angew. Chem., Int. Ed. 2014, 53, 5653; (b) Xuan, J.; Feng, Z.-J.; Chen, J.-R.; Lu, L.-Q.; Xiao, W.-J. Chem. Eur. J. 2014, 20, 3045; (c) Xuan, J.; Zeng, T.-T.; Feng, Z.-J.; Deng, Q.-H.; Chen, J.-R.; Lu, L.-Q.; Xiao, W.-J. Angew. Chem., Int. Ed.2015, 54, 1625; (d) Guo, W.; Lu, L.-Q.; Wang, Y.; Wang, Y.-N.; Chen, J.-R.; Xiao, W.-J. Angew. Chem., Int. Ed. 2015, 54, 2265; (e) Zeng, T.-T.; Xuan, J.; Ding, W.; Wang, K.; Lu, L.-Q.; Xiao, W.-J. Org. Lett. 2015, 17, 4070.
8. [8]
  Zhou, Q.-Q.; Guo, W.; Ding, W.; Wu, X.; Chen, X.; Lu, L.-Q.; Xiao, W.-J. Angew. Chem., Int. Ed. 2015, 54, 11196. doi: 10.1002/anie.201504559
9. [9]
  For the use of hypervalent iodine CN reagent 2a in organic synthesis, see: (a) Zhdankin, V. V.; Kuehl, C. J.; Krasutsky, A. P.; Bolz, J. T.; Mismash, B.; Woodward, J. K.; Simonsen, A. J. Tetrahedron Lett. 1995, 36, 7975; (b) Frei, R.; Courant, T.; Wodrich, M. D.; Waser, J. Chem. Eur. J. 2015, 21, 2662. For representative examples of cyanation reaction using 2b~2d as a cyano source, see: (c) Barton, D. H. R.; Jaszberenyl, J. C.; Theodorakis, E. A. Tetrahedron 1992, 48, 2613; (d) Kim, S.; Song, H. J. Synlett 2002, 2110; (e) Kim, S.; Cho, C. H.; Kim, S.; Uenoyama, Y.; Ryu, I. Synlett 2005, 3160; (f) Gaspar, B.; Carreira, E. M. Angew. Chem., Int. Ed. 2007, 46, 4519; (g) Dai, J.-J.; Zhang, W.-W.; Shu, Y.-J.; Sun, Y.-Y.; Xu, J.; Feng, Y.-S.; Xu, H.-J. Chem. Commun. 2016, 52, 6793; (h) Pawar, A. B.; Chang, S. Org. Lett. 2015, 17, 660; (i) Shu, Z.; Ji, W.; Wang, X.; Zhou, Y.; Zhang, Y.; Wang, J. Angew. Chem., Int. Ed. 2014, 53, 2186.
10. [10]
  For a selected review, see: Xuan, J.; Zhang, Z.-G.; Xiao, W.-J. Angew. Chem., Int. Ed. 2015, 54, 15632.
11. [11]
  For recent examples, see: (a) Huang, H.; Zhang, G.; Chen, Y. Angew. Chem., Int. Ed. 2015, 54, 7872; (b) Tan, H.; Li, H.; Ji, W.; Wang, L. Angew. Chem., Int. Ed. 2015, 54, 8374; (c) Wang, G.-Z.; Shang, R.; Cheng, W.-M.; Fu, Y. Org. Lett. 2015, 17, 4830; (d) Ventre, S.; Petronijevi, F. R.; MacMillan, D. W. C. J. Am. Chem. Soc. 2015, 137, 5654; (e) Zhou, C.; Li, P.-H.; Zhu, X.-J.; Wang, L. Org. Lett. 2015, 17, 6198; (f) Vaillant, F. L.; Courant, T.; Waser, J. Angew. Chem., Int. Ed. 2015, 54, 11200; (g) Griffin, J. D.; Zeller, M. A.; Nicewicz, D. A. J. Am. Chem. Soc. 2015, 137, 11340; (h) Candish, L.; Pitzer, L.; Gomez-Suarez, A.; Glorius, F. Chem. Eur. J. 2016, 22, 4753; (i) Song, H.-T.; Ding, W.; Zhou, Q.-Q.; Liu, J.; Lu, L.-Q.; Xiao, W.-J. J. Org. Chem. 2016, 81, 7250.
12. [12]
  Liu, W.; Ma, Y.; Yin, Y.; Zhao, Y. Bull. Chem. Soc. Jpn. 2006, 79, 577. doi: 10.1246/bcsj.79.577
13. [13]
  Le, C.; MacMillan, D. W. C. J. Am. Chem. Soc. 2015, 137, 11938. doi: 10.1021/jacs.5b08304
14. [14]
  (a) Liu, X.; Wang, Z.; Cheng, X.; Li, C. J. Am. Chem. Soc. 2012, 134, 14330; (b) Huang, H.; Zhang, G.; Gong, L.; Zhang, S.; Chen, Y. J. Am. Chem. Soc. 2014, 136, 2280; (c) Yang, J.; Zhang, J.; Qi, L.; Hu, C.; Chen, Y. Chem. Commun. 2015, 51, 5275.
1. [1]
  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
2. [2]
  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
3. [3]
  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
4. [4]
  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
5. [5]
  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
6. [6]
  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
7. [7]
  Jiao CHEN , Yi LI , Yi XIE , Dandan DIAO , Qiang XIAO . Vapor-phase transport of MFI nanosheets for the fabrication of ultrathin b-axis oriented zeolite membranes. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 507-514. doi: 10.11862/CJIC.20230403
8. [8]
  Wen YANG , Didi WANG , Ziyi HUANG , Yaping ZHOU , Yanyan FENG . La promoted hydrotalcite derived Ni-based catalysts: In situ preparation and CO₂ methanation performance. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 561-570. doi: 10.11862/CJIC.20230276
9. [9]
  Qiangqiang SUN , Pengcheng ZHAO , Ruoyu WU , Baoyue CAO . Multistage microporous bifunctional catalyst constructed by P-doped nickel-based sulfide ultra-thin nanosheets for energy-efficient hydrogen production from water electrolysis. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1151-1161. doi: 10.11862/CJIC.20230454
10. [10]
  Junke LIU , Kungui ZHENG , Wenjing SUN , Gaoyang BAI , Guodong BAI , Zuwei YIN , Yao ZHOU , Juntao LI . Preparation of modified high-nickel layered cathode with LiAlO₂/cyclopolyacrylonitrile dual-functional coating. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1461-1473. doi: 10.11862/CJIC.20240189
11. [11]
  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
12. [12]
  Jing SU , Bingrong LI , Yiyan BAI , Wenjuan JI , Haiying YANG , Zhefeng Fan . Highly sensitive electrochemical dopamine sensor based on a highly stable In-based metal-organic framework with amino-enriched pores. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1337-1346. doi: 10.11862/CJIC.20230414
13. [13]
  Zhihuan XU , Qing KANG , Yuzhen LONG , Qian YUAN , Cidong LIU , Xin LI , Genghuai TANG , Yuqing LIAO . Effect of graphene oxide concentration on the electrochemical properties of reduced graphene oxide/ZnS. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1329-1336. doi: 10.11862/CJIC.20230447
14. [14]
  Kun WANG , Wenrui LIU , Peng JIANG , Yuhang SONG , Lihua CHEN , Zhao DENG . Hierarchical hollow structured BiOBr-Pt catalysts for photocatalytic CO₂ reduction. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1270-1278. doi: 10.11862/CJIC.20240037
15. [15]
  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
16. [16]
  Yuhao SUN , Qingzhe DONG , Lei ZHAO , Xiaodan JIANG , Hailing GUO , Xianglong MENG , Yongmei GUO . Synthesis and antibacterial properties of silver-loaded sod-based zeolite. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 761-770. doi: 10.11862/CJIC.20230169
17. [17]
  Doudou Qin , Junyang Ding , Chu Liang , Qian Liu , Ligang Feng , Yang Luo , Guangzhi Hu , Jun Luo , Xijun Liu . Addressing Challenges and Enhancing Performance of Manganese-based Cathode Materials in Aqueous Zinc-Ion Batteries. Acta Physico-Chimica Sinica, 2024, 40(10): 2310034-. doi: 10.3866/PKU.WHXB202310034
18. [18]
  Zhanggui DUAN , Yi PEI , Shanshan ZHENG , Zhaoyang WANG , Yongguang WANG , Junjie WANG , Yang HU , Chunxin LÜ , Wei ZHONG . Preparation of UiO-66-NH₂ supported copper catalyst and its catalytic activity on alcohol oxidation. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 496-506. doi: 10.11862/CJIC.20230317
19. [19]
  Kai CHEN , Fengshun WU , Shun XIAO , Jinbao ZHANG , Lihua ZHU . PtRu/nitrogen-doped carbon for electrocatalytic methanol oxidation and hydrogen evolution by water electrolysis. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1357-1367. doi: 10.11862/CJIC.20230350
20. [20]
  Yi YANG , Shuang WANG , Wendan WANG , Limiao CHEN . Photocatalytic CO₂ reduction performance of Z-scheme Ag-Cu₂O/BiVO₄ photocatalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 895-906. doi: 10.11862/CJIC.20230434

Get Citation

PDF

XML

Metrics

PDF Downloads(22)
Abstract views(1340)
HTML views(231)

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