Citation: Xiu-Yun Sun, Yong-Hui Sun, Yu Rao. A gram-scale synthesis of multi-substituted arenes via palladium catalyzed C-H halogenation[J]. Chinese Chemical Letters, ;2014, 25(05): 667-669. doi: 10.1016/j.cclet.2014.03.021
-
(6-Amino-2-chloro-3-fluorophenyl)methanol is prepared through both traditional methods and palladium catalyzed iterative C-H halogenation reactions. In comparison to traditional approach, the C-H functionalization strategy demonstrated a few advantages including milder reaction conditions, higher yields, better selectivity and practicality, and high chemical diversity.
-
Keywords:
- Palladium catalysis,
- C-H halogenation,
- Substituted arenes
-
-
[1]
[1] (a) N. Sotomayor, E. Lete, Aryl and heteroaryllithium compounds by metalhalogen exchange. Synthesis of carbocyclic and heterocyclic system, Curr. Org. Chem. 7 (2003) 275-278; (b) A. Butler, J.V. Walker, Marine haloperoxdases, Chem. Rev. 93 (1993) 1937- 1944; (c) S.V. Ley, A.W. Tomas, Modern synthetic methods for copper-mediated C (aryl)- O, C (aryl)-N, and C (aryl)-S bond formation, Angew. Chem. Int. Ed. 42 (2003) 5400- 5449; (d) K.C. Nicolaou, P.G. Bulger, D. Sarlah, Palladium-catalyzed cross-coupling reactions in total synthesis, Angew. Chem. Int. Ed. 44 (2005) 4442-4489; (e) K.C. Nicolaou, P.G. Bulger, D. Sarlah, Palladiumkatalysierte kreuzkupplungen in der total synthese, Angew. Chem. 117 (2005) 4516-4563; (f) J. Hassen,M. Sevignon, C. Gozzi, E. Schulz, M. Lemaire, Aryl-aryl bond formation one century after the discovery of Ullmann reaction, Chem. Rev. 102 (2002) 1359- 1470; (g) Q.L. Shen, T. Ogata, J.F. Hartwig, Highly reactive, general and long-lived catalysts for palladium-catalyzed amination of heteroaryl and aryl chlorides, bromides, and iodides: scope and structure-activity relationships, J. Am. Chem. Soc. 130 (2008) 8564; (h) M. Gorjizadeh, S. Sayyahi, A novel and efficient synthesis of alkyl thiocyanates from alkyl halides in water using phase transfer catalysts, Chin. Chem. Lett. 22 (2011) 659-662; (i) X.Wu, W. Hu, Direct synthesis of diaryl sulfides by copper-catalyzed coupling of aryl halide with aminothiourea, Chin. Chem. Lett. 23 (2012) 391-394.
-
[2]
[2] (a) S. Ma, G. Villa, P.S. Thuy-Boun, A. Homa, J.Q. Yu, Pd-catalyzed ortho-selective C-H deuteration of arenes: evidence for superior reactivity of weakly coordinated palladacycles, Angew. Chem. Int. Ed. 53 (2014) 734-737; (b) K.M. Engle, T.S. Mei, M. Wasa, J.Q. Yu, Weak coordination as a powerful means for developing broadly useful C-H functionalization reactions, Acc. Chem. Res. 45 (2012) 788-802; (c) T.S. Mei, R. Giri, N. Maugel, J.Q. Yu, Pd-catalyzed mono-selective orthohalogenation of C-H bonds assisted by counter cations: an orthogonal method to directed ortho-lithiation, Angew. Chem. Int. Ed. 47 (2008) 5215-5219; (d) X.Y. Sun, Y.H. Sun, C. Zhang, Y. Rao, Room-temperature Pd-catalyzed C-H chlorination by weak coordination: one-pot synthesis of 2-chlorophenols with excellent regioselectivity, Chem. Commun. 50 (2014) 1262-1264; (e) G. Shan, X.L. Yang, L.L. Ma, Y. Rao, Pd-catalyzed C-H oxygenation with TFA/ TFAA: expedient access to oxygen-containing heterocycles and late-stage drug modification, Angew. Chem. Int. Ed. 51 (2012) 13070-13074.
-
[3]
[3] (a) W.E. Parham, C.K. Bradsher, Aromatic organolithuim reagents bearing electrophilic groups. Preparation by halogen-lithuim exchange, Acc. Chem. Res. 15 (1982) 300-305; (b) J. Mortier, J. Moyroud, B. Bennetau, P.A. Cain, The carboxylic acid group as an effective director of ortho-lithiation, J. Org. Chem. 59 (1994) 4042-4044.
-
[4]
[4] X.Y. Sun, G. Shan, Y.H. Sun, Y. Rao, Regio- and chemoselective C-H chlorination/ bromination of electron deficient arenes by weak coordination and study of relative directing-group abilities, Angew. Chem. Int. Ed. 52 (2013) 4440- 4444.
-
[5]
[5] H.H. Xu, C. Wolf, Efficient copper-catalyzed coupling of aryl chlorides, bromides and iodides with aqueous ammonia, Chem. Commun. 21 (2009) 3035-3037.
-
[6]
[6] M.Q. Jia, S.L. You, N-Heterocyclic carbene-catalyzed enantioselective intramolecular N-tethered aldehyde-ketone benzoin reactions, Catalysis 3 (2013) 622-624.
-
[7]
[7] J. Busch-Petersen, T.B. Leonard, M.R. Palovich, et al., Treatment of cystic fibrosis or the symptoms associated with cystic fibrosis, U.S. Pat. Appl. Publ. 20100255167.
-
[8]
[8] C. Tachdjian, D.S. Karanewsky, X.Q. Tang, et al., Modulation of chemosensory receptors and heterobicyclic ligands associated therewith and their preparation, U.S. Pat. Appl. Publ. 20110224155.
-
[9]
[9] A. Blanc, C.G. Bochet, Isotopic effects in photochemistry: application to chromatic orthogonality, Org. Lett. 9 (2007) 2649-2651.
-
[10]
[10] M.P. Storz, C.K. Maurer, C. Zimmer, et al., Validation of PqsD as an anti-biofilm target in Pseudomonas aeruginosa by development of small-molecule inhibitors, J. Am. Chem. Soc. 134 (2012) 16143-16146.
-
[1]
-
-
[1]
Baokang Geng , Xiang Chu , Li Liu , Lingling Zhang , Shuaishuai Zhang , Xiao Wang , Shuyan Song , Hongjie Zhang . High-efficiency PdNi single-atom alloy catalyst toward cross-coupling reaction. Chinese Chemical Letters, 2024, 35(7): 108924-. doi: 10.1016/j.cclet.2023.108924
-
[2]
Haoran Shi , Jiaxin Wang , Yuqin Zhu , Hongyang Li , Guodong Ju , Lanlan Zhang , Chao Wang . Highly selective α-C(sp3)-H arylation of alkenyl amides via nickel chain-walking catalysis. Chinese Chemical Letters, 2024, 35(7): 109333-. doi: 10.1016/j.cclet.2023.109333
-
[3]
Yi Luo , Lin Dong . Multicomponent remote C(sp2)-H bond addition by Ru catalysis: An efficient access to the alkylarylation of 2H-imidazoles. Chinese Chemical Letters, 2024, 35(10): 109648-. doi: 10.1016/j.cclet.2024.109648
-
[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]
Jie Yang , Xin-Yue Lou , Dihua Dai , Jingwei Shi , Ying-Wei Yang . Desymmetrized pillar[8]arenes: High-yield synthesis, functionalization, and host-guest chemistry. Chinese Chemical Letters, 2025, 36(1): 109818-. doi: 10.1016/j.cclet.2024.109818
-
[6]
Conghui Wang , Lei Xu , Zhenhua Jia , Teck-Peng Loh . Recent applications of macrocycles in supramolecular catalysis. Chinese Chemical Letters, 2024, 35(4): 109075-. doi: 10.1016/j.cclet.2023.109075
-
[7]
Wei Chen , Pieter Cnudde . A minireview to ketene chemistry in zeolite catalysis. Chinese Journal of Structural Chemistry, 2024, 43(11): 100412-100412. doi: 10.1016/j.cjsc.2024.100412
-
[8]
Hailong He , Wenbing Wang , Wenmin Pang , Chen Zou , Dan Peng . Double stimulus-responsive palladium catalysts for ethylene polymerization and copolymerization. Chinese Chemical Letters, 2024, 35(7): 109534-. doi: 10.1016/j.cclet.2024.109534
-
[9]
Gongcheng Ma , Qihang Ding , Yuding Zhang , Yue Wang , Jingjing Xiang , Mingle Li , Qi Zhao , Saipeng Huang , Ping Gong , Jong Seung Kim . Palladium-free chemoselective probe for in vivo fluorescence imaging of carbon monoxide. Chinese Chemical Letters, 2024, 35(9): 109293-. doi: 10.1016/j.cclet.2023.109293
-
[10]
Yu Mao , Yilin Liu , Xiaochen Wang , Shengyang Ni , Yi Pan , Yi Wang . Acylfluorination of enynes via phosphine and silver catalysis. Chinese Chemical Letters, 2024, 35(8): 109443-. doi: 10.1016/j.cclet.2023.109443
-
[11]
Jiaqi Jia , Kathiravan Murugesan , Chen Zhu , Huifeng Yue , Shao-Chi Lee , Magnus Rueping . Multiphoton photoredox catalysis enables selective hydrodefluorinations. Chinese Chemical Letters, 2025, 36(2): 109866-. doi: 10.1016/j.cclet.2024.109866
-
[12]
Tong Li , Leping Pan , Yan Zhang , Jihu Su , Kai Li , Kuiliang Li , Hu Chen , Qi Sun , Zhiyong Wang . Electrochemical construction of 2,5-diaryloxazoles via N–H and C(sp3)-H functionalization. Chinese Chemical Letters, 2024, 35(4): 108897-. doi: 10.1016/j.cclet.2023.108897
-
[13]
Min Fu , Pan He , Sen Zhou , Wenqiang Liu , Bo Ma , Shiying Shang , Yaohao Li , Ruihan Wang , Zhongping Tan . An unexpected stereochemical effect of thio-substituted Asp in native chemical ligation. Chinese Chemical Letters, 2024, 35(8): 109434-. doi: 10.1016/j.cclet.2023.109434
-
[14]
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
-
[15]
Ning LI , Siyu DU , Xueyi WANG , Hui YANG , Tao ZHOU , Zhimin GUAN , Peng FEI , Hongfang MA , Shang JIANG . Preparation and efficient catalysis for olefins epoxidation of a polyoxovanadate-based hybrid. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 799-808. doi: 10.11862/CJIC.20230372
-
[16]
Uttam Pandurang Patil . Porous carbon catalysis in sustainable synthesis of functional heterocycles: An overview. Chinese Chemical Letters, 2024, 35(8): 109472-. doi: 10.1016/j.cclet.2023.109472
-
[17]
Liliang Chu , Xiaoyan Zhang , Jianing Li , Xuelei Deng , Miao Wu , Ya Cheng , Weiping Zhu , Xuhong Qian , Yunpeng Bai . Continuous-flow synthesis of polysubstituted γ-butyrolactones via enzymatic cascade catalysis. Chinese Chemical Letters, 2024, 35(4): 108896-. doi: 10.1016/j.cclet.2023.108896
-
[18]
Hao-Cong Li , Ming Zhang , Qiyan Lv , Kai Sun , Xiao-Lan Chen , Lingbo Qu , Bing Yu . Homogeneous catalysis and heterogeneous separation: Ionic liquids as recyclable photocatalysts for hydroacylation of olefins. Chinese Chemical Letters, 2025, 36(2): 110579-. doi: 10.1016/j.cclet.2024.110579
-
[19]
Ke-Ai Zhou , Lian Huang , Xing-Ping Fu , Li-Ling Zhang , Yu-Ling Wang , Qing-Yan Liu . Fluorinated metal-organic framework for methane purification from a ternary CH4/C2H6/C3H8 mixture. Chinese Journal of Structural Chemistry, 2023, 42(11): 100172-100172. doi: 10.1016/j.cjsc.2023.100172
-
[20]
Jingping Hu , Jing Xu . Total synthesis of a putative yuzurimine-type Daphniphyllum alkaloid C14–epi-deoxycalyciphylline H. Chinese Chemical Letters, 2024, 35(4): 108733-. doi: 10.1016/j.cclet.2023.108733
-
[1]
Metrics
- PDF Downloads(0)
- Abstract views(663)
- HTML views(21)