Citation: Xu Shuying, Chen Xiaojia, Li Jihui, Xu Wenrong, Zhang Yucang. Recent Advances in Transition Metal-Catalyzed Synthesis of Guanidines[J]. Chinese Journal of Organic Chemistry, ;2016, 36(9): 1985-1993. doi: 10.6023/cjoc201604036 shu

Recent Advances in Transition Metal-Catalyzed Synthesis of Guanidines

Xu Shuying ^a ,
Chen Xiaojia ^b ,
Li Jihui ^a,*,, ,
Xu Wenrong ^a ,
Zhang Yucang ^a,*,,

a.
College of Materials and Chemical Engineering, Hainan University, Haikou 570228
b.
Products Quality Supervision and Testing Institute of Hainan Province, Haikou 570003

Corresponding author: Li Jihui, lijihui@hainu.edu.cn Zhang Yucang, zhangyucang88@163.com
Received Date: 18 April 2016
Revised Date: 16 May 2016

Fund Project: the Natural Science Fundation of Hainan Province 20162015the Hainan Province International Science and Technology Specific KJHZ2014-02the Research Fund for the Doctoral Program of Higher Education of China 20134601110004the Natural Science Fundation of Hainan Province 20152027

Figures(9)

Guanidines are a unique class of tri-nitrogen compounds having various bioactivities, which are wildly presented in natural products and drug molecules, and they are wildly used in pharmacy and pesticide fields. Moreover, they have high application value in organic synthesis and functional materials. The synthesis of guanidines has received much attention due to their unique structures and widespread application value. Recently, lots of new synthetic methods of guanidines, especially the synthetic methods based on highly efficient transition metal-catalyzed reactions, have been developed. The recent progress in transition metal-catalyzed reactions developed for the synthesis of guanidines in the past twenty years is summarized. The synthetic methods for various guanidines are introduced comprehensively, and the characteristics and disadvantages of these methods are also discussed, thus it may be helpful for the research on transition metal-catalyzed synthesis of guanidines.
- transition metal-catalyzed,
- C-N formation reaction,
- guanidines,
- synthetic method
1. [1]
  Tapiero, H.;Mathé, G.;Couvreur, P.;Tew, K.D.Biomed.Pharmacother.2002, 56, 439. doi: 10.1016/S0753-3322(02)00284-6
2. [2]
  Heys, L.;Moore, C.G.; Murphy, P.J.Chem.Soc.Rev.2000, 29, 57.
  (b) Urban, S.;Leone, P.A.; Carroll, A.R.; Fechner, G.A.; Smith, J.;Hooper, J.N.A.; Quinn, R.J.J.Org.Chem.1999, 64, 731.
  (c) Hensler, M.E.; Bernstein, G.;Nizeta, V.;Nefzi, A.Bioorg.Med.Chem.Lett.2006, 16, 5073.
  (d) Masuda, T.;Shibuya, S.;Arai, M.;Yoshida, S.;Tomozawa, T.;Ohno, A.;Yamashitab, M.;Honda, T.Bioorg.Med.Chem.Lett.2003, 13, 669.
3. [3]
  Selig, P.Synthesis 2013, 45, 703. doi: 10.1055/s-00000084
4. [4]
  Karmel, I.S.R.; Fridman, N.;Tamm, M.;Eisen, M.S.J.Am.Chem.Soc.2014, 136, 17180. doi: 10.1021/ja5091436
5. [5]
  Cao, Y.-J.; Gao, H.-X.; Lu, R.-H.Chin.J.Synth.Chem.2003, 11, 193(in Chinese).
  (曹玉娟, 高海翔, 鲁润华, 合成化学, 2003, 11, 19.)
  (b) Shen, Z.-X.; Wang, Y.-L.; Zhang, Y.-W.Chin.J.Org.Chem.2002, 22, 388(in Chinese).
  (沈宗旋, 王亚玲, 张雅文, 有机化学, 2002, 22, 388.)
  (c) Ma, Y.;De, S.;Chen, C.Tetrahedron 2015, 71, 1145.
6. [6]
  Ni, C.;Zhu, L.;Hu, J.Acta Chem.Sinica 2015, 73, 90(in Chinese).
  (倪传法, 朱林桂, 胡金波, 化学学报, 2015, 73, 90.)
  (b) Zhang, W.;Dai, J.;Xu, H.Chin.J.Org.Chem.2015, 35, 1820(in Chinese).
  (张文曼, 戴建军, 许华建, 有机化学, 2015, 35, 1820.)
7. [7]
  Lu, B.;Li, X.;Lin, Y.Chin.J.Org.Chem.2015, 35, 2275(in Chinese).
8. [8]
  Tan, M.;Gu, Y.;Luo, X.;Zhang, P.Chin.J.Org.Chem.2015, 35, 781(in Chinese). doi: 10.6023/cjoc201409046
9. [9]
  Qin, Y.;Peng, Q.Chin.J.Org.Chem.2011, 31, 1169(in Chinese).
10. [10]
  Xie, J.;Zhou, Q.Acta Chem.Sinica 2012, 70, 1427(in Chinese).
  (谢建华, 周其林, 化学学报, 2012, 70, 1427.)
  (b) Zhao, Y.;Guo, C.;Wu, H.Prog.Chem.2014, 26, 345(in Chinese).
  (赵艳, 郭彩红, 武海顺, 化学进展, 2014, 26, 345.)
11. [11]
  Zhuo, Z.;Wang, T.;Zhou, X.;Zhang, H.Chin.J.Org.Chem.2014, 34, 1471(in Chinese).
  (卓庆德, 王铜道, 周小茜, 张弘, 有机化学, 2014, 34, 1471.)
  (b) Liao, G.;Shi, B.Acta Chim.Sinica 2015, 73, 1283(in Chinese).
  (廖港, 史炳锋, 化学学报, 2015, 73, 1283.)
12. [12]
  Cortes-Salva, M.;Nguyen, B.-L.; Cuevas, J.;Pennypacker, K.R.; Antilla, J.C.Org.Lett.2010, 12, 1316. doi: 10.1021/ol1002175
13. [13]
  Xing, H.;Zhang, Y.;Lai, Y.;Jiang, Y.;Ma, D.J.Org.Chem.2012, 77, 5449. doi: 10.1021/jo300840x
14. [14]
  Miyabe, H.;Yoshida, K.;Reddy, V.K.; Takemoto, Y.J.Org.Chem.2009, 74, 305. doi: 10.1021/jo802271d
15. [15]
  Zhong, M.;Bui, M.;Shen, W.;Baskaran, S.;Allen, D.A.; Elling, R.A.; Flanagan, W.M.; Fung, A.D.; Hanan, E.J.; Harris, S.O.; Heumann, S.A.; Hoch, U.;Ivy, S.N.; Jacobs, J.W.; Lam, S.;Lee, H.;McDowell, R.S.; Oslob, J.D.; Purkey, H.E.; Romanowski, M.J.; Silverman, J.A.; Tangonan, B.T.; Taverna, P.;Yang, W.;Yoburn, J.C.; Yu, C.H.; Zimmerman, K.M.; O'Brien, T.;Lew, W.Biol.Med.Chem.Lett.2009, 19, 5158.
  (b) Moriya, M.;Kishino, H.;Sakuraba, S.;Sakamoto, T.;Suga, T.;Takahashi, H.;Suzuki, T.;Ito, M.;Ito, J.;Moriya, R.;Takenaga, N.;Iwaasa, H.;Ishihara, A.;Kanatani, A.;Fukami, T.Biol.Med.Chem.Lett.2009, 19, 3568.
  (c) Lo, H.Y.; Bentzien, J.;Fleck, R.W.; Pullen, S.S.Biol.Med.Chem.Lett.2008, 18, 6218.
  (d) Xuan, G.;Han, J.;Li X.Eur.J.Med.Chem.2006, 41, 1080.
  (e) Pérez-Villanueva, J.;Hernández-Campos, A.;Yépez-Mulia, L.Biol.Med.Chem.2013, 21, 4221.
  (f) Chen, J.;Gao, L.-X.; Gong, J.-X.; Jiang, C.-S.; Yao, L.-G.; Li, J.-Y.; Li, J.;Xiao, W.;Guo, Y.-W.Biol.Med.Chem.2015, 23, 2211.
16. [16]
  Ueda, S.;Buchwald, S.L.Angew.Chem., Int.Ed.2012, 51, 10364.
  (b) Almaşi, D.;Alonso, D.A.; Gómez-Bengoa, E.;Nájera, C.J.Org.Chem.2009, 74, 6163.
  (c) Zhang, L.;Lee, M.-M.; Lee, S.-M.; Lee J.; Cheng, M.;Jeong, B.-S.; Park, H.-G.; Jew, S.-S.Adv.Synth.Catal.2009, 351, 3063.
  (d) Gómez-Torres, E.;Alonso, D.A.; Gómez-Bengoa, E.;Nájera, C.Org.Lett.2011, 13, 6106.
17. [17]
  Rastogi, R.;Sharma, S.Synthesis 1983, 861.
  (b) Cee, V.J.; Downing, N.S.Tetrahedron Lett.2006, 47, 3747.
  (c) Xie, Y.;Zhang, F.;Li, J.;Shi, X.Synlett 2010, 901.
  (d) Deasy, R.E.; Slattery, C.N.; Maguire, A.R.; Kjell, D.P.; Hawk, M.K.N.; Joo, J.M.; Gu, R.L.; Moynihan, H.J.Org.Chem.2014, 45, 3688.
  (e) Artman, G.D.Ⅲ; Solovay, C.F.; Adams, C.M.; Diaz, B.;Dimitroff, M.;Ehara, T.;Gu, D.;Ma, F.;Liu, D.;Miller, B.R.; Pick, T.E.; Poon, D.J.; Ryckman, D.;Siesel, D.A.; Stillwell, B.S.; Swiftney, T.;Dyck, J.P.; Zhang, C.;Ji, N.Tetrahedron Lett.2010, 51, 5319.
  (f) Pollock, J.A.; Kim, S.H.; Katzenellenbogen, J.A.Tetrahedron Lett.2015, 56, 6097.
18. [18]
  Evindar, G.;Batey, R.A.Org.Lett.2003, 5, 133. doi: 10.1021/ol027061h
19. [19]
  Chi, Y.;Zhang, W.-X.; Xi, Z.Org.Lett.2014, 16, 6274. doi: 10.1021/ol502815p
20. [20]
  Ueda, S.;Buchwald, S.L.Angew.Chem., Int.Ed.2012, 51, 10364. doi: 10.1002/anie.201204710
21. [21]
  Kim, M.;Mulcahy, J.V.; Espino, C.G.; Bois, J.D.Org.Lett.2006, 8, 1073. doi: 10.1021/ol052920y
22. [22]
  Muñiz, K.;Martínez, C.J.Org.Chem.2013, 78, 2168. doi: 10.1021/jo302472w
23. [23]
  Schultz, D.M.; Wolfe, J.P.Synthesis (Stuttg)2012, 44, 351.
  (b) Wolfe, J.P.Synlett 2008, 2913.
  (c) Wolfe, J.P.Synlett 2006, 571.
24. [24]
  Gainer, M.J.; Bennett, N.R.; Takahashi, Y.;Looper, R.E.Angew.Chem., Int.Ed.2011, 50, 684. doi: 10.1002/anie.v50.3
25. [25]
  Hövelmann, C.H.; Streuff, J.;Brelot, L.;Muñiz, K.Chem.Commun.2008, 28, 2334.
26. [26]
  Zavesky, B.P.; Babij, N.R.; Fritz, J.A.; Wolfe, J.P.Org.Lett.2013, 15, 5420. doi: 10.1021/ol402377y
27. [27]
  Zavesky, B.P.; Babij, N.R.; Wolfe, J.P.Org.Lett.2014, 16, 4952. doi: 10.1021/ol502471x
28. [28]
  Li, J.;Neuville, L.Org.Lett.2013, 15, 6124. doi: 10.1021/ol4029622
29. [29]
  Li, J.;Wang, H.;Hou, Y.;Yu, W.;Xu, S.;Zhang, Y.Eur.J.Org.Chem.2016, 2388.
30. [30]
  Wang, F.;Cai, S.;Liao, Q.;Xi, C.J.Org.Chem.2011, 76, 3174. doi: 10.1021/jo200014v
31. [31]
  Yu, H.;Liu, Q.;Li, Y.;Ni, C.Tetrahedron Lett.2012, 53, 5253. doi: 10.1016/j.tetlet.2012.07.072
32. [32]
  He, H.-F.; Wang, Z.-J.; Bao, W.Adv.Synth.Catal.2010, 352, 2905. doi: 10.1002/adsc.v352.17
33. [33]
  Tran, L.Q.; Li, J.;Neuville, L.J.Org.Chem.2015, 80, 6102. doi: 10.1021/acs.joc.5b00614
34. [34]
  Wang, Q.;Schreiber, S.L.Org.Lett.2009, 11, 5178. doi: 10.1021/ol902079g
35. [35]
  Cohen, F.;Overman, L.E.J.Am.Chem.Soc.2001, 123, 10782.
  (b) Arnold, M.A.; Day, K.A.; Duron, S.G.; Gin, D.Y.J.Am.Chem.Soc.2006, 128, 13255.
  (c) Evans, P.A.; Qin, J.;Robinson, J.E.; Bazin, B.Angew.Chem., Int.Ed.2007, 46, 7417.
  (d) Ishiwata, T.;Hino, T.;Koshino, H.;Hashimoto, Y.;Nakata, T.;Nagasawa, K.Org.Lett.2002, 4, 2921.
  (e) Rodriguez, R.A.; Steed, D.B.; Kawamata, Y.;Su, S.;Smith, T.C.; Steed, P.A.; Romesberg, F.E.; Baran, P.S.J.Am.Chem.Soc.2014, 136, 15403.
  (f) Ma, Z.;Wang, X.;Ma, Y.;Chen, C.Angew.Chem., Int.Ed.2016, 55, 4763.
36. [36]
  Babij, N.R.; Wolfe, J.P.Angew.Chem., Int.Ed.2012, 51, 4128. doi: 10.1002/anie.201201001
37. [37]
  Babij, N.R.; Wolfe, J.P.Angew.Chem., Int.Ed.2013, 52, 9247. doi: 10.1002/anie.201302720
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]
  Lin′an CAO , Dengyue MA , Gang XU . Research advances in electrically conductive metal-organic frameworks-based electrochemical sensors. Chinese Journal of Inorganic Chemistry, 2025, 41(10): 1953-1972. doi: 10.11862/CJIC.20250160
3. [3]
  Xiangyu CHEN , Zhenzhen MIAO , Ligang XU , Guangbao WU , Zhuang LIU , Wenzhen LÜ , Runfeng CHEN . Research progress on low-dimensional organic-inorganic hybrid metal halide optoelectronic materials. Chinese Journal of Inorganic Chemistry, 2025, 41(11): 2201-2217. doi: 10.11862/CJIC.20250056
4. [4]
  Yan Li , Xinze Wang , Xue Yao , Shouyun Yu . 基于激发态手性铜催化的烯烃E→Z异构的动力学拆分——推荐一个本科生综合化学实验. University Chemistry, 2024, 39(5): 1-10. doi: 10.3866/PKU.DXHX202309053
5. [5]
  Yanhui Guo , Li Wei , Zhonglin Wen , Chaorong Qi , Huanfeng Jiang . Recent Progress on Conversion of Carbon Dioxide into Carbamates. Acta Physico-Chimica Sinica, 2024, 40(4): 2307004-0. doi: 10.3866/PKU.WHXB202307004
6. [6]
  Rongzhan LOU , Qiaoling KANG , Zhenchao BAI , Dongyun LI , Yang XU , Rui WANG , Qingyi LU . Research progress of sodium ion high entropy layered oxide cathode. Chinese Journal of Inorganic Chemistry, 2025, 41(12): 2411-2428. doi: 10.11862/CJIC.20250142
7. [7]
  Lu Zhuoran , Li Shengkai , Lu Yuxuan , Wang Shuangyin , Zou Yuqin . Cleavage of C―C Bonds for Biomass Upgrading on Transition Metal Electrocatalysts. Acta Physico-Chimica Sinica, 2024, 40(4): 2306003-0. doi: 10.3866/PKU.WHXB202306003
8. [8]
  Mengyang LI , Zhonghao NIU , Hao XU , Jingli XIE . One-pot synthesis of 4H-pyran derivatives catalyzed by viologen-modified metal-organic frameworks. Chinese Journal of Inorganic Chemistry, 2026, 42(7): 1513-1522. doi: 10.11862/CJIC.20250205
9. [9]
  Jia-He Li , Yu-Ze Liu , Jia-Hui Ma , Qing-Xiao Tong , Jian-Ji Zhong , Jing-Xin Jian . 洛芬碱衍生物的合成、化学发光与重金属离子检测. University Chemistry, 2025, 40(6): 230-237. doi: 10.12461/PKU.DXHX202407080
10. [10]
  Jinxing CAO , Rubing QIU , Hongyong ZHU , Rongrong LI , Yuanxin JI , Xiaoyu ZHANG , Hui ZHANG . Research progress on the synthesis method of ion-doped copper sulfide and its applications in photocatalysis and energy fields. Chinese Journal of Inorganic Chemistry, 2026, 42(3): 453-466. doi: 10.11862/CJIC.20250295
11. [11]
  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
12. [12]
  Ying Wang , Mingcheng Yang , Zhu Yin , Yingqi Wang , Jiajia Cheng . Transition metal-free poly(heptazine imide) photocatalyst for C-X bond construction from katritzky salts. Acta Physico-Chimica Sinica, 2026, 42(7): 100212-. doi: 10.1016/j.actphy.2025.100212
13. [13]
  Lixing ZHANG , Yaowen WANG , Xu HAN , Junhong ZHOU , Jinghui WANG , Liping LI , Guangshe LI . Research progress in the synthesis of fluorine-containing perovskites and their derivatives. Chinese Journal of Inorganic Chemistry, 2025, 41(9): 1689-1701. doi: 10.11862/CJIC.20250007
14. [14]
  Longfei MA , Fang SI , Congjie PAN , Xinhua WANG . Synthesis and crystal structure of extended tetrathiafulvalene derivatives and cupric bromide charge transfer complexes. Chinese Journal of Inorganic Chemistry, 2026, 42(6): 1229-1236. doi: 10.11862/CJIC.20250355
15. [15]
  Wenliang Wang , Weina Wang , Tian Sheng , Nan Wei , Sufan Wang , Tao Zhou . 过渡金属/氧化物催化CO₂加H₂还原生成甲醇的甲酸盐与甲酰基路径的前线轨道对称性分析. University Chemistry, 2026, 41(9): 405-411. doi: 10.12461/PKU.DXHX202508059
16. [16]
  Xiaofei Liu , He Wang , Li Tao , Weimin Ren , Xiaobing Lu , Wenzhen Zhang . Electrocarboxylation of Benzylic Phosphates and Phosphinates with Carbon Dioxide. Acta Physico-Chimica Sinica, 2024, 40(9): 2307008-0. doi: 10.3866/PKU.WHXB202307008
17. [17]
  Yan Qi , Yueqin Yu , Weisi Guo , Yongjun Liu . 过渡金属参与的有机反应案例教学与实践探索. University Chemistry, 2025, 40(6): 111-117. doi: 10.12461/PKU.DXHX202411021
18. [18]
  Ruizhi Duan , Xiaomei Wang , Panwang Zhou , Yang Liu , Can Li . The role of hydroxyl species in the alkaline hydrogen evolution reaction over transition metal surfaces. Acta Physico-Chimica Sinica, 2025, 41(9): 100111-0. doi: 10.1016/j.actphy.2025.100111
19. [19]
  Yonghui ZHOU , Rujun HUANG , Dongchao YAO , Aiwei ZHANG , Yuhang SUN , Zhujun CHEN , Baisong ZHU , Youxuan ZHENG . Synthesis and photoelectric properties of fluorescence materials with electron donor-acceptor structures based on quinoxaline and pyridinopyrazine, carbazole, and diphenylamine derivatives. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 701-712. doi: 10.11862/CJIC.20230373
20. [20]
  Chunyan Hu , Wei Wang , Zewei Mao , Mei Zhang , Lei Zhang , Yuping Lin . Three-stage progressive teaching reform and practice in organic chemistry experiments for pharmacy undergraduates: synthesis of coumarin-chalcone derivatives. University Chemistry, 2026, 41(7): 282-289. doi: 10.12461/PKU.DXHX202505011

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(3460)
HTML views(733)

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