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

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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
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