Citation: Zhang Yong, Yang hongzhen, Yu Xinling, Cheng Xu, Li Weijian, Guo Lingmei, Hai Li, Guo Li, Wu Yong. Room Temperature Ru(Ⅲ)-Catalyzed ortho-Hydroxymethylation of Arenes[J]. Chinese Journal of Organic Chemistry, ;2018, 38(12): 3211-3218. doi: 10.6023/cjoc201805022 shu

Room Temperature Ru(Ⅲ)-Catalyzed ortho-Hydroxymethylation of Arenes

Key Laboratory of Drug-Targeting of Education Ministry and Department of Medicinal Chemistry, West China School of Pharmacy, Sichuan University, Chengdu 610041

Corresponding author: Guo Li, guoli@scu.edu.cn Wu Yong, wyong@scu.edu.cn
Received Date: 9 May 2018
Revised Date: 31 July 2018
Available Online: 5 December 2018
Fund Project: the National Natural Science Foundation of China 81573286Project supported by the National Natural Science Foundation of China (Nos. 81373259, 81573286, 81602954)the National Natural Science Foundation of China 81602954the National Natural Science Foundation of China 81373259

Figures(2)

Direct synthesis of the hydroxymethylated arene derivatives via ruthenium(Ⅲ)-catalyzed nitrogen atom directed C-H activation is described. The reaction proceeds smoothly at room temperature and generates the corresponding products in moderate to excellent yields. Meanwhile, it has a broad substrate scope and opens up an attractive avenue for the application of direct hydroxymethylation in the synthesis of biologically active compounds.
- C-H activation,
- paraformaldehyde,
- hydroxymethylation,
- room temperature
1. [1]
  (a) Collin, D. T.; Hartley, D.; Jack, D.; Lunts, L. H.; Press, J. C.; Ritchie, A. C.; Toon, P. J. Med. Chem. 1970, 13, 674.
  (b) Schachter, E. N. Drugs Today 2010, 46, 911.
  (c) Gomelsky, A.; Dmochowski, R. R. Drugs Today 2010, 46, 81.
  (d) Filho, R. P.; de Souza Menezes, C. M.; Pinto, P. L.; Paula, G. A.; Brandt, C. A.; da Silveira, M. A. Bioorg. Med. Chem. 2007, 15, 1229.
  (e) Zhang, J. S.; Zhu, D. Y.; Hong, S. H. Phytochemistry 1995, 39, 435.
2. [2]
  Select example: Bouveault, L. Bull. Soc. Chim. Fr. 1903, 29, 1051.
3. [3]
  Select example: Mettler, C. Ber. Dtsch. Chem. Ges. 1905, 38, 1745.
4. [4]
  (a) Vavon, G. Anal. Chim. 1914, 1, 144.
  (b) Raber, D. J.; Guida, W. C.; Shoenberger, D. C. Tetrahedron Lett. 1981, 22, 4077.
5. [5]
  (a) Nystrom, R. F.; Chaikin, S. W.; Brown, W. G. J. Am. Chem. Soc. 1949, 71, 3245.
  (b) Santaniello, E. J. Org. Chem. 1981, 46, 4584.
  (c) Brown, H. C.; Choi, Y. M. Synthesis 1981, 439.
6. [6]
  (a) Cardillo, G.; Orena, M.; Porzi, G.; Sandri, S. Synthesis 1981, 793.
  (b) Chemla, F.; Normant, J. Tetrahedron Lett. 1995, 36, 3157.
  (c) Hu, Y. L.; Jiang, H.; Zhu, J.; Lu, M. New J. Chem. 2011, 35, 292.
7. [7]
  (a) Raber, D. J.; Guida, W. C. J. Org. Chem. 1976, 41, 690.
  (b) Santaniello, E.; Fiecchi, A.; Manzocchi, A.; Ferraboschi, P. J. Org. Chem. 1983, 48, 3074.
8. [8]
  Flippin, L. A.; Gallagher, D. W.; Jalali-Araghi, K. J. Org. Chem. 1989, 54, 1430. doi: 10.1021/jo00267a035
9. [9]
  (a) Kamochi, Y.; Kudo, T. Chem. Lett. 1993, 9, 1495.
  (b) Fisher, G. B. J. Org. Chem. 1994, 59, 6378.
10. [10]
  Kamitanaka, T.; Yamamoto K.; Matsuda, T. Tetrahedron 2008, 64, 5699. doi: 10.1016/j.tet.2008.04.029
11. [11]
  (a) Wu, Y. Q. Tetrahedron Lett. 2000, 41, 2847.
  (b) Reddy, M. A. New. J. Chem. 2001, 25, 359.
  (c) Cadot, C. Tetrahedron Lett. 2002, 43, 1839.
  (d) Markovic, D.; Vogel, P. Org. Lett. 2004, 6, 2693.
12. [12]
  Molander, G. A.; Cavalcanti, L. N. J. Org. Chem. 2011, 76, 623. doi: 10.1021/jo102208d
13. [13]
  (a) Kawamoto, T. Org. Lett. 2013, 15, 2144.
  (b) Molla, R. A. Green Chem. 2016, 18, 4649.
14. [14]
  Khusnutdinova, J. R.; Milstein, Y. B-D. Angew. Chem., Int. Ed. 2013, 52, 6269. doi: 10.1002/anie.201301000
15. [15]
  Hydroxymethylation of carbonyl substrates see: (a) Ito, Y.; Sawamura, M.; Shirakawa, E.; Hayashizaki, K.; Hayashi, T. Tetrahedron Lett. 1988, 29, 235.
  (b) Torii, H.; Nakadai, M.; Ishihara, K.; Saito S.; Yamamoto, H. Angew. Chem., Int. Ed. 2004, 43, 1983.
  (c) Kuhl N.; Glorius, F. Chem. Commun. 2011, 47, 573.
  (d) Shirakawa, S.; Ota, K.; Terao S. J.; Maruoka, K. Org. Biomol. Chem. 2012, 10, 5753.
16. [16]
  Reductive hydroxymethylation of allenes, alkenes and alkynes see: (a) Ngai, M.-Y.; Skucas, E.; Krische, M. J. Org. Lett. 2008, 10, 2705.
  (b) Sam, B.; Montgomery, T. P.; Krische, M. J. Org. Lett. 2013, 15, 3790.
  (c) Kopfer, A.; Sam, B.; Breit B.; Krische, M. J. Chem. Sci. 2013, 4, 1876.
  (d) Bausch, C. C.; Patman, R. L.; Breit, B.; Krische, M. J. Angew. Chem., Int. Ed. 2011, 50, 5687.
17. [17]
  Hydromethoxylation of boronic acids see: (a) Yamamoto, T.; Zhumagazin, A.; Furusawa, T.; Tanaka, R.; Yamakawa, T.; Oe Y.; Ohta, T. Adv. Synth. Catal. 2014, 356, 3525.
  (b) Kawamoto, T.; Fukuyama, T.; Ryz, I. J. Am. Chem. Soc. 2012, 134, 875.
  (c) Kawamoto, T.; Ryu, I. Chimia 2012, 66, 372.
18. [18]
  (a) Maruyama, K.; Kubo, K.; Toda, Y.; Kawase, K.; Mashino, T.; Nishinaga, A. Tetrahedron Lett. 1995, 36, 5609.
  (b) Khan, A.; Zheng, R.; Kan, Y.; Ye, J.; Xing J.; Zhang, Y. J. Angew. Chem., Int. Ed. 2014, 53, 6439.
  (c) Xie, Y.; Hu, J.; Wang, Y.; Xia, C.; Huang, H. J. Am. Chem. Soc. 2012, 134, 20613.
  (d) Zhang, G.; Gao, B.; Huang, H. Angew. Chem., Int. Ed. 2015, 54, 7657-7661.
19. [19]
  (a) Morimoto, T.; Fujioka, M.; Fuji, K.; Tsutsumi K.; Kakiuchi, K. J. Organomet. Chem. 2007, 692, 625.
  (b) Liu, Q.; Wu, L.; Jackstell, R.; Beller, M. ChemCatChem 2014, 6, 2805.
  (c) Kusumoto, S.; Tatsuki T.; Nozaki, K. Angew. Chem., Int. Ed. 2015, 54, 8458.
20. [20]
  (a) Pyo, A.; Kim, S.; Kumar, M. R.; Byeun, A.; Eom, M. S.; Han, M. S.; Lee, S. Tetrahedron Lett. 2013, 54, 5207.
  (b) Heim, L. E.; Schloer, N. E.; Choi, J.-H.; Prechtl, M. H. G. Nat. Commun. 2014, 5, 3621.
  (c) Suenobu, T.; Isaka, Y.; Shibata, S.; Fukuzumi, S. Chem. Commun. 2015, 51, 1670.
21. [21]
  (a) Saidi, O.; Bamford, M. J.; Blacker, A. J.; Lynch, J.; Marsden, S. P.; Plucinski, P.; Watson, R. J.; Williams, J. M. J. Tetrahedron Lett. 2010, 51, 5804.
  (b) Zhang, J.; Hong, S. H. Org. Lett. 2012, 14, 4646.
  (c) Lee, H.; Kang, B.; Lee, S.-I.; Hong, S. H. Synlett 2015, 1077.
22. [22]
  (a) Watanabe, Y.; Yamamoto, M.; Mitsudo, T.-A.; Takegami, Y. Tetrahedron Lett. 1978, 19, 1289.
  (b) Man, N. Y. T.; Li, W.; Stewart, S. G.; Wu, X.-F. Chimia 2015, 69, 345.
23. [23]
  Li, W. F.; Wu, X. F. Adv. Synth. Catal. 2015, 357, 3393. doi: 10.1002/adsc.201500753
24. [24]
  Cheng, X. F.; Wang, H. M.; Xiao, F. H.; Deng, G. J. Green Chem. 2016, 18, 5773. doi: 10.1039/C6GC02319C
25. [25]
  Zhang, G. F.; Li, Y.; Xie, X. Q.; Ding, C. R. Org. Lett. 2017, 19, 1216. doi: 10.1021/acs.orglett.7b00183
26. [26]
  Wu, Y. X.; Zhou, B. ACS Catal. 2017, 7, 2213. doi: 10.1021/acscatal.7b00078
27. [27]
  Zhang, Y.; Yang, Z. Z.; Guo, L. M.; Li, W. J.; Cheng, X.; Wang, X. L.; Wang, Q. T.; Hai, L.; Wu, Y. Org. Chem. Front. 2018, 5, 1604. doi: 10.1039/C8QO00193F
1. [1]
  Wei-Bin Li , Xiao-Chao Huang , Pei Liu , Jie Kong , Guo-Ping Yang . Recent advances in directing group assisted transition metal catalyzed para-selective C-H functionalization. Chinese Chemical Letters, 2025, 36(6): 110543-. doi: 10.1016/j.cclet.2024.110543
2. [2]
  Chao Chen , Wenwen Yu , Guangen Huang , Xuelian Ren , Xiangli Chen , Yixin Li , Shenggui Liang , Mengmeng Xu , Mingyue Zheng , Yaxi Yang , He Huang , Wei Tang , Bing Zhou . Asymmetric macrocyclization enabled by Rh(Ⅲ)-catalyzed CH activation: Enantioenriched macrocyclic inhibitor of Zika virus infection. Chinese Chemical Letters, 2024, 35(11): 109574-. doi: 10.1016/j.cclet.2024.109574
3. [3]
  Dian-Xue Ma , Yu-Wu Zhong . Achieving highly-efficient room-temperature phosphorescence with a nylon matrix. Chinese Journal of Structural Chemistry, 2024, 43(9): 100391-100391. doi: 10.1016/j.cjsc.2024.100391
4. [4]
  Shulei Hu , Yu Zhang , Xiong Xie , Luhan Li , Kaixian Chen , Hong Liu , Jiang Wang . Rh(Ⅲ)-catalyzed late-stage C-H alkenylation and macrolactamization for the synthesis of cyclic peptides with unique Trp(C7)-alkene crosslinks. Chinese Chemical Letters, 2024, 35(8): 109408-. doi: 10.1016/j.cclet.2023.109408
5. [5]
  Xin Li , Jia-Min Lu , Bo Li , Chen Zhao , Bei-Bei Yang , Li Li . Chiroptical sensing for remote chiral amines via a C–H activation reaction. Chinese Chemical Letters, 2025, 36(5): 110310-. doi: 10.1016/j.cclet.2024.110310
6. [6]
  Kun Zhang , Ni Dan , Dan-Dan Ren , Ruo-Yu Zhang , Xiaoyan Lu , Ya-Pan Wu , Li-Lei Zhang , Hong-Ru Fu , Dong-Sheng Li . A small D-A molecule with highly heat-resisting room temperature phosphorescence for white emission and anti-counterfeiting. Chinese Journal of Structural Chemistry, 2024, 43(3): 100244-100244. doi: 10.1016/j.cjsc.2024.100244
7. [7]
  Shiqi Peng , Yongfang Rao , Tan Li , Yufei Zhang , Jun-ji Cao , Shuncheng Lee , Yu Huang . Regulating the electronic structure of Ir single atoms by ZrO₂ nanoparticles for enhanced catalytic oxidation of formaldehyde at room temperature. Chinese Chemical Letters, 2024, 35(7): 109219-. doi: 10.1016/j.cclet.2023.109219
8. [8]
  Jiayin Zhou , Depeng Liu , Longqiang Li , Min Qi , Guangqiang Yin , Tao Chen . Responsive organic room-temperature phosphorescence materials for spatial-time-resolved anti-counterfeiting. Chinese Chemical Letters, 2024, 35(11): 109929-. doi: 10.1016/j.cclet.2024.109929
9. [9]
  Shuai Zhu , Mingjie Chen , Haichao Shen , Hanming Ding , Wenbo Li , Junliang Zhang . Palladium/Xu-Phos-catalyzed enantioselective arylalkoxylation reaction of γ-hydroxyalkenes at room temperature. Chinese Chemical Letters, 2024, 35(11): 109879-. doi: 10.1016/j.cclet.2024.109879
10. [10]
  Jianmei Guo , Yupeng Zhao , Lei Ma , Yongtao Wang . Ultra-long room temperature phosphorescence, intrinsic mechanisms and application based on host-guest doping systems. Chinese Journal of Structural Chemistry, 2024, 43(9): 100335-100335. doi: 10.1016/j.cjsc.2024.100335
11. [11]
  Zeyin Chen , Jiaju Shi , Yusheng Zhou , Peng Zhang , Guodong Liang . Polymer microparticles with ultralong room-temperature phosphorescence for visual and quantitative detection of oxygen through phosphorescence image and lifetime analysis. Chinese Chemical Letters, 2025, 36(5): 110629-. doi: 10.1016/j.cclet.2024.110629
12. [12]
  Hong Yao , Feixiang Yang , Jianpeng Hu , Wenyu Cao , Shuning Qin , Tai-Bao Wei , Bingbing Shi , Qi Lin . Ultralong room temperature phosphorescence and broad color-tunability persistent luminescence via new strategy. Chinese Chemical Letters, 2025, 36(6): 110375-. doi: 10.1016/j.cclet.2024.110375
13. [13]
  Hai-Yang Song , Jun Jiang , Yu-Hang Song , Min-Hang Zhou , Chao Wu , Xiang Chen , Wei-Min He . Supporting-electrolyte-free electrochemical [2 + 2 + 1] annulation of benzo[d]isothiazole 1,1-dioxides, N-arylglycines and paraformaldehyde. Chinese Chemical Letters, 2024, 35(6): 109246-. doi: 10.1016/j.cclet.2023.109246
14. [14]
  Qian Wang , Ting Gao , Xiwen Lu , Hangchao Wang , Minggui Xu , Longtao Ren , Zheng Chang , Wen Liu . Nanophase separated, grafted alternate copolymer styrene-maleic anhydride as an efficient room temperature solid state lithium ion conductor. Chinese Chemical Letters, 2024, 35(7): 108887-. doi: 10.1016/j.cclet.2023.108887
15. [15]
  Xin Li , Ling Zhang , Yunyan Fan , Shaojing Lin , Yong Lin , Yongsheng Ying , Meijiao Hu , Haiying Gao , Xianri Xu , Zhongbiao Xia , Xinchuan Lin , Junjie Lu , Xiang Han . Carbon interconnected microsized Si film toward high energy room temperature solid-state lithium-ion batteries. Chinese Chemical Letters, 2025, 36(2): 109776-. doi: 10.1016/j.cclet.2024.109776
16. [16]
  Sheng Zhao , Junjie Lu , Bifu Sheng , Siying Zhang , Hao Li , Jizhang Chen , Xiang Han . High-performance room temperature solid-state lithium battery enabled by PP-PVDF multilayer composite electrolyte. Chinese Chemical Letters, 2025, 36(6): 110008-. doi: 10.1016/j.cclet.2024.110008
17. [17]
  Qiao Song , Xue Peng , Zhouyu Wang , Leyong Wang . Iron-catalyzed C–H activation: A sustainable approach to efficient organic synthesis. Chinese Chemical Letters, 2025, 36(5): 110869-. doi: 10.1016/j.cclet.2025.110869
18. [18]
  Tao Tang , Chen Li , Sipu Li , Zhong Qiu , Tianqi Yang , Beirong Ye , Shaojun Shi , Chunyang Wu , Feng Cao , Xinhui Xia , Minghua Chen , Xinqi Liang , Xinping He , Xin Liu , Yongqi Zhang . One-step constructing advanced N-doped carbon@metal nitride as ultra-stable electrocatalysts via urea plasma under room temperature. Chinese Chemical Letters, 2024, 35(11): 109887-. doi: 10.1016/j.cclet.2024.109887
19. [19]
  Yu-Yao Li , Xiao-Hui Li , Zhi-Xuan An , Yang Chu , Xiu-Li Wang . Room-temperature olefin epoxidation reaction by two 2D cobalt metal-organic complexes under O₂ atmosphere: Coordination and structural regulation. Chinese Chemical Letters, 2025, 36(4): 109716-. doi: 10.1016/j.cclet.2024.109716
20. [20]
  Lu Dai , Yuxin Ren , Shuang Li , Meidi Wang , Chentao Hu , Ya-Pan Wu , Guangtong Hai , Dong-Sheng Li . Room-temperature synthesis of Co(OH)₂/Mo₂TiC₂T_x hetero-nanosheets with interfacial coupling for enhanced oxygen evolution reaction. Chinese Chemical Letters, 2025, 36(4): 109774-. doi: 10.1016/j.cclet.2024.109774

Get Citation

PDF

XML

Metrics

PDF Downloads(3)
Abstract views(736)
HTML views(34)

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