Citation: Li Xue-Fei, Lin Jin-Shun, Wang Jian, Li Zhong-Liang, Gu Qiang-Shuai, Liu Xin-Yuan. Cu/Chiral Phosphoric Acid-Catalyzed Asymmetric Radical-Initiated Aminoarylation of Alkenes[J]. Acta Chimica Sinica, ;2018, 76(11): 878-882. doi: 10.6023/A18100413 shu

Cu/Chiral Phosphoric Acid-Catalyzed Asymmetric Radical-Initiated Aminoarylation of Alkenes

a.
Department of Chemistry and Shenzhen Grubbs Institute, Southern University of Science and Technology, Shenzhen 518055
b.
SUSTech Academy for Advanced Interdisciplinary Studies, Southern University of Science and Technology, Shenzhen 518055

Corresponding author: Gu Qiang-Shuai, guqs@sustc.edu.cn Liu Xin-Yuan, liuxy3@sustc.edu.cn
Received Date: 7 October 2018
Available Online: 15 November 2018
Fund Project: the Shenzhen Special Funds JCYJ20170307105638498the National Natural Science Foundation of China 21722203Project supported by the National Natural Science Foundation of China (Nos. 21722203, 21572096), the Shenzhen Special Funds (Nos. JCYJ20170412152435366, JCYJ20170307105638498) and the Shenzhen Nobel Prize Scientists Laboratory Project (No. C17213101)the Shenzhen Special Funds JCYJ20170412152435366the Shenzhen Nobel Prize Scientists Laboratory Project C17213101the National Natural Science Foundation of China 21572096

Figures(4)

Enantioenriched pyrrolidines bearing a β-aryl group and an α-quaternary carbon stereocenter are important structural motifs in many natural products and pharmaceuticals, and their enantioselective synthesis has thus received extensive attention over the last several decades. Nonetheless, so far as we know, asymmetric aminoarylation of alkenes to access such targets has only been independently reported by Wolfe and Liu using palladium catalysis involving a key aminopalladation step, and thus, general and practical methodologies towards a variety of chiral pyrrolidines are still in demand and highly desirable. As part of our ongoing interest in radical-initiated difunctionalization reactions of alkenes based on Cu(I)/chiral phosphoric acid (CPA) catalysis, we sought to develop a mechanistically distinct and complementary approach for this asymmetric palladium(Ⅱ)-catalyzed aminoarylation of alkenes. Herein we describe our efforts toward the development of the efficient asymmetric radical-initiated aminoarylation of alkenes with aryldiazonium salts enabled by Cu(I)/CPA catalysis. A general procedure for the aminoarylation of alkenes with aryldiazonium salts is as follows:under argon, an oven-dried resealable Schlenk tube equipped with a magnetic stir bar was charged with urea substrate 1 (0.1 mmol, 1.0 equiv.), CuI (1.9 mg, 0.01 mmol, 10 mol%), CPA[(S)-A1 (9.3 mg, 0.015 mmol, 15 mol%], aryldiazonium salts 2 (0.12 mmol, 1.2 equiv.), Na₃PO₄ (19.7 mg, 0.12 mmol, 1.2 equiv.) and isopropyl acetate(1.0 mL) at 32℃ and the sealed tube was then stirred under the same conditions. Upon completion (monitored by thin-layer chromatography), the reaction mixture was directly purified by silica gel chromatography[eluent:V(petroleum ether):V(EtOAc)=100:0 to 3:1] to afford the desired product 3. The enantiometric excess of product was determined by chiral high-performance liquid chromatography (HPLC) analysis. A broad scope of substrates worked well under this standard conditions to afford enantioenriched pyrrolidines in good yield with good to excellent enantioselectivity. A series of control experiments were conducted to determine the reaction mechanism as a radical process and a possible mechanism was proposed.
- copper catalysis,
- chiral phosphoric acid,
- radical,
- aryldiazonium salts,
- asymmetric aminoarylation
1. [1]
  (a) Royles, B. J. L. Chem. Rev. 1995, 95, 1981; (b) O'Hagan, D. Nat. Prod. Rep. 2000, 17, 435. (c) Lewis, J. R. Nat. Prod. Rep. 2001, 18, 95. (d) Fish, P. V.; Andrews, M. D.; Jonathan Fray, M.; Stobie, A.; Wakenhut, F.; Whitlock, G. A. Bioorg. Med. Chem. Lett. 2009, 19, 2829.
2. [2]
  (a) Fache, F.; Schulz, E.; Tommasino, M. L.; Lemaire, M. Chem. Rev. 2000, 100, 2159. (b) Notz, W.; Tanaka, F.; Barbas, C. F. Acc. Chem. Res. 2004, 37, 580. (c) Erkkila, A.; Majander, I.; Pihko, P. M. Chem. Rev. 2007, 107, 5416. (d) Caputo, C. A.; Jones, N. D. Dalton Trans. 2007, 4627.
3. [3]
  (a) Pettit, G. R.; Goswami, A.; Cragg, G. M.; Schmidt, J. M.; Zou, J. C. J. Nat. Prod. 1984, 47, 913. (b) Su, B.; Cai, C.; Deng, M.; Wang, Q. J. Agric. Food. Chem. 2016, 64, 2039.
4. [4]
  Oloff, S.; Mailman, R. B.; Tropsha, A. J. Med. Chem. 2005, 48, 7322. doi: 10.1021/jm049116m
5. [5]
  Burnett, D. A.; Hart, D. J. J. Org. Chem. 1987, 52, 5662. doi: 10.1021/jo00235a004
6. [6]
  Lebon, F.; Pegurier, C.; Ledecq, M.; Mathieu, B.; Bosman, N.; Frycia, A.; Lengele, S.; Dhurke, K.; Kanduluru, A. K.; Meunier, S.; Wagner, A.; Wolff, C.; Provins, L. Bioorg. Med. Chem. Lett. 2012, 22, 3978. doi: 10.1016/j.bmcl.2012.04.097
7. [7]
  For selected reviews, see: (a) Coldham, I.; Hufton, R. Chem. Rev. 2005, 105, 2765. (b) Pandey, G.; Banerjee, P.; Gadre, S. R. Chem. Rev. 2006, 106, 4484. (c) Pellissier, H. Tetrahedron 2007, 63, 3235. (d) Nicolle, S. M.; Lewis, W.; Hayes, C. J.; Moody, C. J. Angew. Chem., Int. Ed. 2016, 55, 3749.
8. [8]
9. [9]
  For selected reviews, see: (a) Heinrich, M. R. Chem. Eur. J. 2009, 15, 820. (b) Hari, D. P.; Koenig, B. Angew. Chem., Int. Ed. 2013, 52, 4734. (c) Kindt, S.; Heinrich, M. R. Synthesis 2016, 48, 1597.
10. [10]
  For selected examples, see: (a) Sahoo, B.; Hopkinson, M. N.; Glorius, F. J. Am. Chem. Soc. 2013, 135, 5505. (b) Hari, D. P.; Hering, T.; Koenig, B. Angew. Chem., Int. Ed. 2014, 53, 725. (c) Kindt, S.; Wicht, K.; Heinrich, M. R. Org. Lett. 2015, 17, 6122.
11. [11]
  (a) Mai, D. N.; Wolfe, J. P. J. Am. Chem. Soc. 2010, 132, 12157. (b) Babij, N. R.; Wolfe, J. P. Angew. Chem., Int. Ed. 2013, 52, 9247. (c) Hopkins, B. A.; Wolfe, J. P. Chem. Sci. 2014, 5, 4840. (d) White, D. R.; Hutt, J. T.; Wolfe, J. P. J. Am. Chem. Soc. 2015, 137, 11246. (e) Garlets, Z. J.; Parenti, K. R.; Wolfe, J. P. Chem.-Eur. J. 2016, 22, 5919.
12. [12]
  Zhang, W.; Chen, P.; Liu, G. Angew. Chem., Int. Ed. 2017, 56, 5336. doi: 10.1002/anie.201700889
13. [13]
  (a) Neukom, J. D.; Perch, N. S.; Wolfe, J. P. J. Am. Chem. Soc. 2010, 132, 6276. (b) Neukom, J. D.; Perch, N. S.; Wolfe, J. P. Organometallics 2011, 30, 1269.
14. [14]
  Zhu, R.; Buchwald, S. L. J. Am. Chem. Soc. 2015, 137, 8069. doi: 10.1021/jacs.5b04821
15. [15]
  Lin, J.-S.; Dong, X.-Y.; Li, T.-T.; Jiang, N.-C.; Tan, B.; Liu, X.-Y. J. Am. Chem. Soc. 2016, 138, 9357. doi: 10.1021/jacs.6b04077
16. [16]
  Lin, J.-S.; Wang, F.-L.; Dong, X.-Y.; He, W.-W.; Yuan, Y.; Chen, S.; Liu, X.-Y. Nat. Commun. 2017, 8, 14841. doi: 10.1038/ncomms14841
17. [17]
  Wang, F.-L.; Dong, X.-Y.; Lin, J.-S.; Zeng, Y.; Jiao, G.-Y.; Gu, Q.-S.; Guo, X.-Q.; Ma, C.-L.; Liu, X.-Y. Chem 2017, 3, 979. doi: 10.1016/j.chempr.2017.10.008
18. [18]
  (a) Wang, F.; Wang, D.; Wan, X.; Wu, L.; Chen, P.; Liu, G. J. Am. Chem. Soc. 2016, 138, 15547. (b) Wang, D.; Wang, F.; Chen, P.; Lin, Z.; Liu, G. Angew. Chem., Int. Ed. 2017, 56, 2054. (c) Wu, L.; Wang, F.; Wan, X.; Wang, D.; Chen, P.; Liu, G. J. Am. Chem. Soc. 2017, 139, 2904.
19. [19]
  Cheng, Y.-F.; Dong, X.-Y.; Gu, Q.-S.; Yu, Z.-L.; Liu, X.-Y. Angew. Chem., Int. Ed. 2017, 56, 8883. doi: 10.1002/anie.v56.30
1. [1]
  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
2. [2]
  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
3. [3]
  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
4. [4]
  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
5. [5]
  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
6. [6]
  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
7. [7]
  Youlin SI , Shuquan SUN , Junsong YANG , Zijun BIE , Yan CHEN , Li LUO . Synthesis and adsorption properties of Zn(Ⅱ) metal-organic framework based on 3, 3', 5, 5'-tetraimidazolyl biphenyl ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1755-1762. doi: 10.11862/CJIC.20240061
8. [8]
  Hong LI , Xiaoying DING , Cihang LIU , Jinghan ZHANG , Yanying RAO . Detection of iron and copper ions based on gold nanorod etching colorimetry. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 953-962. doi: 10.11862/CJIC.20230370
9. [9]
  Qiuyang LUO , Xiaoning TANG , Shu XIA , Junnan LIU , Xingfu YANG , Jie LEI . Application of a densely hydrophobic copper metal layer in-situ prepared with organic solvents for protecting zinc anodes. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1243-1253. doi: 10.11862/CJIC.20240110
10. [10]
  Wenlong LI , Xinyu JIA , Jie LING , Mengdan MA , Anning ZHOU . Photothermal catalytic CO₂ hydrogenation over a Mg-doped In₂O_3-x catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 919-929. doi: 10.11862/CJIC.20230421
11. [11]
  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
12. [12]
  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
13. [13]
  Juan WANG , Zhongqiu WANG , Qin SHANG , Guohong WANG , Jinmao LI . NiS and Pt as dual co-catalysts for the enhanced photocatalytic H₂ production activity of BaTiO₃ nanofibers. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1719-1730. doi: 10.11862/CJIC.20240102
14. [14]
  Peiran ZHAO , Yuqian LIU , Cheng HE , Chunying DUAN . A functionalized Eu³⁺ metal-organic framework for selective fluorescent detection of pyrene. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 713-724. doi: 10.11862/CJIC.20230355
15. [15]
  Ruolin CHENG , Haoran WANG , Jing REN , Yingying MA , Huagen LIANG . Efficient photocatalytic CO₂ cycloaddition over W₁₈O₄₉/NH₂-UiO-66 composite catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 523-532. doi: 10.11862/CJIC.20230349
16. [16]
  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
17. [17]
  Yan LIU , Jiaxin GUO , Song YANG , Shixian XU , Yanyan YANG , Zhongliang YU , Xiaogang HAO . Exclusionary recovery of phosphate anions with low concentration from wastewater using a CoNi-layered double hydroxide/graphene electronically controlled separation film. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1775-1783. doi: 10.11862/CJIC.20240043
18. [18]
  Zhiwen HU , Weixia DONG , Qifu BAO , Ping LI . Low-temperature synthesis of tetragonal BaTiO₃ for piezocatalysis. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 857-866. doi: 10.11862/CJIC.20230462
19. [19]
  Guimin ZHANG , Wenjuan MA , Wenqiang DING , Zhengyi FU . Synthesis and catalytic properties of hollow AgPd bimetallic nanospheres. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 963-971. doi: 10.11862/CJIC.20230293
20. [20]
  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

Get Citation

PDF

XML

Metrics

PDF Downloads(36)
Abstract views(944)
HTML views(173)

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