Citation: Meng-Yan Liu, Shi-Bin Hong, Wei Zhang, Wei Deng. Expedient copper-catalyzed borylation reactions using amino acids as ligands[J]. Chinese Chemical Letters, ;2015, 26(3): 373-376. doi: 10.1016/j.cclet.2014.12.004 shu

Expedient copper-catalyzed borylation reactions using amino acids as ligands

Meng-Yan Liu ^a,b ,
Shi-Bin Hong ^a,b ,
Wei Zhang ^a,b ,
Wei Deng ^a,b,,

1.
a Research Center of Nano Science and Technology, Shanghai University, Shanghai 200444, China;
2.
b School of Chemical and Engineering, Shanghai Institute of Technology, Shanghai 201418, China

Corresponding author: Wei Deng,
Received Date: 1 September 2014
Available Online: 24 November 2014
Fund Project: We gratefully acknowledge financial support from the Eastern Scholar, Shanghai Pujiang Program, Key Subject of Shanghai Municipal Education Commission, Natural Science Foundation of Shanghai (No. 12ZR1410500) (No. 12ZR1410500)

Amino acids were found to be as good ligands for copper-catalyzed borylation reactions of primary and secondary alkyl halides, and the B₂pin₂ acted as bi-boron source for borylation. The high reaction efficiency and mild conditions make the new catalyst system a useful alternative to the recently developed methods for the preparation of alkylboronic esters.
- Cu-catalyzed,
- Borylation,
- Amino acid,
- Alkylboronic,
- Organoboron
1. [1]
  [1] T.C. Atack, R.M. Lecker, A.P. Cook, Iron-catalyzed borylation of alkyl electrophiles, J. Am. Chem. Soc. 136 (2014) 9521-9523.
2. [2]
  [2] (a) P.J. Unsworth, D. Leonori, V.K. Aggarwal, Stereocontrolled synthesis of 1,5-stereogenic centers through three-carbon homologation of boronic esters, Angew. Chem. Int. Ed. 53 (2014) 9846-9850; (b) K.L. Billingsley, T.E. Barder, S.L. Buchwald, Palladium-catalyzed borylation of aryl chlorides: scope, applications, and computational studies, Angew. Chem. 119 (2007) 5455-5459; (c) M.A. Larsen, J.F. Hartwig, Iridium-catalyzed C-H borylation of heteroarenes: scope, regioselectivity, application to late-stage functionalization, and mechanism, J. Am. Chem. Soc. 136 (2014) 4287-4299; (d) C.W. Liskey, J.F. Hartwig, Iridium-catalyzed C-H borylation of cyclopropanes, J. Am. Chem. Soc. 135 (2013) 3375-3378; (e) L.S. Zhang, G.H. Chen, X. Wang, et al., Direct borylation of primary C-H bonds in functionalized molecules by palladium catalysis, Angew. Chem. 126 (2014) 3980-3984; (f) J. Yu, L. Zhang, G.B. Yan, Metal-free, visible light-induced borylation of aryldiazonium salts: a simple and green synthetic route to arylboronates, Adv. Synth. Catal. 354 (2012) 2625-2628; (g) C.T. Yang, Z.Q. Zhang, Y.C. Liu, L. Liu, Copper-catalyzed cross-coupling reaction of organoboron compounds with primary alkyl halides and pseudohalides, Angew. Chem. Int. Ed. 50 (2011) 3904-3907; (h) G.B. Yan, Y.B. Jiang, C.X. Kuang, et al., Nano-Fe₂O₃-catalyzed direct borylation of arenes, Chem. Commun. 46 (2010) 3170-3172.
3. [3]
  [3] For selected work on the copper-catalyzed reactions, see: (a) X. Zhang, H. Yi, Z.X. Liao, et al., Copper-catalysed direct radical alkenylation of alkyl bromides, Org. Biomol. Chem. 12 (2014) 6790-6793; (b) X.Y. Li, B.J. Li, J.S. You, J.B. Lan, Copper-catalysed oxidative C-H/N-H crosscoupling between formamides and amides through chelation-assisted N-H activation, Org. Biomol. Chem. 11 (2013) 1925-1928; (c) C.T. Yang, Z.Q. Zhang, J. Liang, et al., Copper-catalyzed cross-coupling of nonactivated secondary alkyl halides and tosylates with secondary alkyl Grignard reagents, J. Am. Chem. Soc. 134 (2012) 11124-11127.
4. [4]
  [4] N. Miyaura, A. Suzuki, Palladium-catalyzed cross-coupling reactions of organoboron compounds, Chem. Rev. 95 (1995) 2457-2483.
5. [5]
  [5] C.T. Yang, Z.Q. Zhang, H. Tajuddin, et al., Alkylboronic esters from copper-catalyzed borylation of primary and secondary alkyl halides and pseudohalides, Angew. Chem. Int. Ed. 51 (2012) 528-532.
6. [6]
  [6] (a) W. Deng, Y.F. Wang, Y. Zou, L. Liu, Q.X. Guo, Amino acid-mediated Goldberg reactions between amides andaryl iodides, Tetrahedron Lett.45 (2004) 2311-2315; (b) W. Deng, Y. Zou, Y.F. Wang, L. Liu, Q.X. Guo, CuI-catalyzed coupling reactions of aryl iodides and bromides with thiols promoted by amino acid ligands, Synlett (2004) 1254-1258; (c) W. Deng, L. Liu, C. Zhang, M. Liu, Q.X. Guo, Copper-catalyzed cross-coupling of sulfonamides with aryl iodides and bromides facilitated by amino acid ligands, Tetrahedron Lett. 46 (2005) 7295-7298; (d) X. Cui, Z. Li, C.Z. Tao, et al., N,N-dimethyl-b-alanine as an inexpensive and efficient ligand for palladium-catalyzed Heck reaction, Org. Lett. 8 (2006) 2467-2470; (e) X. Cui, J. Li, Z.P. Zhang, et al., Pd(quinoline-8-carboxylate)2 as a low-priced, phosphine-free catalyst for Heck and Suzuki reactions, J. Org. Chem. 72 (2007) 9342-9345.
7. [7]
  [7] C. Kleeberg, Z.Y. Lin, T.B. Marder, A facile route to aryl boronates: room-temperature, copper-catalyzed borylation of aryl halides with alkoxy diboron reagents, Angew. Chem. 121 (2009) 5454-5458.
8. [8]
  [8] For selected work on amino acids and their derivatives as ligands in synthetic organic chemistry, see: (a) D.W. Ma, Q. Cai, Copper/amino acid catalyzed cross-couplings of aryl and vinyl halides with nucleophiles, Acc. Chem. Res. 41 (2008) 1450-1460; (b) D.W. Ma, Q. Cai, H. Zhang, Mild method for Ullmann coupling reaction of amines and aryl halides, Org. Lett. 5 (2003) 2453-2455; (c) J.S. Zheng, H.N. Chang, F.L. Wang, L. Liu, Fmoc synthesis of peptide thioesters without post-chain-assembly manipulation, J. Am. Chem. Soc. 133 (2011) 11080-11083; (d) S. Gladiali, E. Alberico, Asymmetric transfer hydrogenation: chiral ligands and applications, Chem. Soc. Rev. 35 (2006) 226-236; (e) C.T. Yang, Y. Fu, Y.B. Huang, et al., Room-temperature copper-catalyzed carbon-nitrogen coupling of aryl iodides and bromides promoted by organic ionic bases, Angew. Chem. Int. Ed. 48 (2009) 7398-7401.
9. [9]
  [9] For selected work on boryllithium, see: (a) Y. Segawa, Y. Suzuki, M. Yamashita, K. Nozaki, Chemistry of boryllithium: synthesis, structure, and reactivity, J. Am. Chem. Soc. 130 (2008) 16069-16079; (b) P. Jaramillo, P. Pérez, P. Fuentealba, Chemical reactivity descriptors for ambiphilic reagents: dual descriptor, local hypersoftness, and electrostatic potentia, J. Phys. Chem. A 113 (2009) 6812-6817; (c) K. Nozaki, Y. Aramaki, M. Yamashita, S.H. Ueng, M.M. Curran, Boryltrihydroborate: synthesis, structure, and reactivity as a reductant in ionic, organometallic, and radical reactions, J. Am. Chem. Soc. 132 (2010) 11449-11451.
10. [10]
  [10] A. Boneta, V. Lilloa, J. Ramíreza, M.M. Requejob, E. Fernández, The selective catalytic formation of b-boryl aldehydes through a base-free approach, Org. Biomol. Chem. 7 (2009) 1533-1535.
1. [1]
  Xiang Huang , Dongzhen Xu , Yang Liu , Xia Huang , Yangfan Wu , Dongmei Fang , Bing Xia , Wei Jiao , Jian Liao , Min Wang . Asymmetric synthesis of difluorinated α-quaternary amino acids (DFAAs) via Cu-catalyzed difluorobenzylation of aldimine esters. Chinese Chemical Letters, 2024, 35(12): 109665-. doi: 10.1016/j.cclet.2024.109665
2. [2]
  Wujun Jian , Mong-Feng Chiou , Yajun Li , Hongli Bao , Song Yang . Cu-catalyzed regioselective diborylation of 1,3-enynes for the efficient synthesis of 1,4-diborylated allenes. Chinese Chemical Letters, 2024, 35(5): 108980-. doi: 10.1016/j.cclet.2023.108980
3. [3]
  Bowen Wang , Longwu Sun , Qianqian Cao , Xinzhi Li , Jianai Chen , Shizhao Wang , Miaolin Ke , Fener Chen . Cu-catalyzed three-component CSP coupling for the synthesis of trisubstituted allenyl phosphorothioates. Chinese Chemical Letters, 2024, 35(12): 109617-. doi: 10.1016/j.cclet.2024.109617
4. [4]
  Qian Ren , Xue Dai , Ran Cen , Yang Luo , Mingyang Li , Ziyun Zhang , Qinghong Bai , Zhu Tao , Xin Xiao . A cucurbit[8]uril-based supramolecular phosphorescent assembly: Cell imaging and sensing of amino acids in aqueous solution. Chinese Chemical Letters, 2024, 35(12): 110022-. doi: 10.1016/j.cclet.2024.110022
5. [5]
  Yiyue Ding , Qiuxiang Zhang , Lei Zhang , Qilu Yao , Gang Feng , Zhang-Hui Lu . Exceptional activity of amino-modified rGO-immobilized PdAu nanoclusters for visible light-promoted dehydrogenation of formic acid. Chinese Chemical Letters, 2024, 35(7): 109593-. doi: 10.1016/j.cclet.2024.109593
6. [6]
  Zhen Liu , Zhi-Yuan Ren , Chen Yang , Xiangyi Shao , Li Chen , Xin Li . Asymmetric alkenylation reaction of benzoxazinones with diarylethylenes catalyzed by B(C₆F₅)₃/chiral phosphoric acid. Chinese Chemical Letters, 2024, 35(5): 108939-. doi: 10.1016/j.cclet.2023.108939
7. [7]
  Yulin Mao , Jingyu Ma , Jiecheng Ji , Yuliang Wang , Wanhua Wu , Cheng Yang . Crown aldoxime ethers: Their synthesis, structure, acid-catalyzed/photo-induced isomerization and adjustable guest binding. Chinese Chemical Letters, 2024, 35(11): 109927-. doi: 10.1016/j.cclet.2024.109927
8. [8]
  Jiajun Lu , Zhehui Liao , Tongxiang Cao , Shifa Zhu . Synergistic Brønsted/Lewis acid catalyzed atroposelective synthesis of aryl-β-naphthol. Chinese Chemical Letters, 2025, 36(1): 109842-. doi: 10.1016/j.cclet.2024.109842
9. [9]
  Xinghui Yao , Zhouyu Wang , Da-Gang Yu . Sustainable electrosynthesis: Enantioselective electrochemical Rh(III)/chiral carboxylic acid-catalyzed oxidative CH cyclization coupled with hydrogen evolution reaction. Chinese Chemical Letters, 2024, 35(9): 109916-. doi: 10.1016/j.cclet.2024.109916
10. [10]
  Kaimin WANG , Xiong GU , Na DENG , Hongmei YU , Yanqin YE , Yulu MA . Synthesis, structure, fluorescence properties, and Hirshfeld surface analysis of three Zn(Ⅱ)/Cu(Ⅱ) complexes based on 5-(dimethylamino) isophthalic acid. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1397-1408. doi: 10.11862/CJIC.20240009
11. [11]
  Chuan-Zhi Ni , Ruo-Ming Li , Fang-Qi Zhang , Qu-Ao-Wei Li , Yuan-Yuan Zhu , Jie Zeng , Shuang-Xi Gu . A chiral fluorescent probe for molecular recognition of basic amino acids in solutions and cells. Chinese Chemical Letters, 2024, 35(10): 109862-. doi: 10.1016/j.cclet.2024.109862
12. [12]
  Chong Liu , Ling Li , Jiahui Gao , Yanwei Li , Nazhen Zhang , Jing Zang , Cong Liu , Zhaopei Guo , Yanhui Li , Huayu Tian . The study of antibacterial activity of cationic poly(β-amino ester) regulating by amphiphilic balance. Chinese Chemical Letters, 2025, 36(2): 110118-. doi: 10.1016/j.cclet.2024.110118
13. [13]
  Anqiu LIU , Long LIN , Dezhi ZHANG , Junyu LEI , Kefeng WANG , Wei ZHANG , Junpeng ZHUANG , Haijun HAO . Synthesis, structures, and catalytic activity of aluminum and zinc complexes chelated by 2-((2,6-dimethylphenyl)amino)ethanolate. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 791-798. doi: 10.11862/CJIC.20230424
14. [14]
  Zhen Dai , Linzhi Tan , Yeyu Su , Kerui Zhao , Yushun Tian , Yu Liu , Tao Liu . Site-specific incorporation of reduction-controlled guest amino acids into proteins for cucurbituril recognition. Chinese Chemical Letters, 2024, 35(5): 109121-. doi: 10.1016/j.cclet.2023.109121
15. [15]
  Wenhao Wang , Siyuan Peng , Zhengwei Huang , Xin Pan . Tuning amino/hydroxyl ratios of nanovesicles to manipulate protein corona-mediated in vivo fate. Chinese Chemical Letters, 2024, 35(11): 110134-. doi: 10.1016/j.cclet.2024.110134
16. [16]
  Min-Hang Zhou , Jun Jiang , Wei-Min He . EDA-complexes-enabled photochemical synthesis of α-amino acids with imines and tetrabutylammonium oxalate. Chinese Chemical Letters, 2025, 36(1): 110446-. doi: 10.1016/j.cclet.2024.110446
17. [17]
  Zhili Li , Qijun Wo , Dongdong Huang , Dezhong Zhou , Lei Guo , Yeqing Mao . Improving gene transfection efficiency of highly branched poly(β-amino ester)s through the in-situ conversion of inactive terminal groups. Chinese Chemical Letters, 2024, 35(8): 109737-. doi: 10.1016/j.cclet.2024.109737
18. [18]
  Jia-Cheng Hou , Hong-Tao Ji , Yu-Han Lu , Jia-Sheng Wang , Yao-Dan Xu , Yan-Yan Zeng , Wei-Min He . Sustainable and practical semi-heterogeneous photosynthesis of 5-amino-1,2,4-thiadiazoles over WS₂/TEMPO. Chinese Chemical Letters, 2024, 35(8): 109514-. doi: 10.1016/j.cclet.2024.109514
19. [19]
  Wenyi Mei , Lijuan Xie , Xiaodong Zhang , Cunjian Shi , Fengzhi Wang , Qiqi Fu , Zhenjiang Zhao , Honglin Li , Yufang Xu , Zhuo Chen . Design, synthesis and biological evaluation of fluorescent derivatives of ursolic acid in living cells. Chinese Chemical Letters, 2024, 35(5): 108825-. doi: 10.1016/j.cclet.2023.108825
20. [20]
  Huipeng Zhao , Xiaoqiang Du . Polyoxometalates as the redox anolyte for efficient conversion of biomass to formic acid. Chinese Journal of Structural Chemistry, 2024, 43(2): 100246-100246. doi: 10.1016/j.cjsc.2024.100246

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(599)
HTML views(30)

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