Copper-Catalyzed Amination of Vinyl Azides to α-Ketoamides

Yu Wang; Dongling Zhang; Kaining Zhang; Zhenhua Liu; Jing Lin; Wei Cao; Zhongxue Fang

doi:10.1055/s-0037-1611922

SynOpen, Inhaltsverzeichnis

CC BY ND NC 4.0 · SynOpen 2019; 03(04): 91-95
DOI: 10.1055/s-0037-1611922

letter

Copyright with the author(s) (2019) The author(s)

Copper-Catalyzed Amination of Vinyl Azides to α-Ketoamides

Autoren

Yu Wang

^aSchool of Chemistry and Environmental Engineering, Yancheng Teachers University, Yancheng224007, P. R. of China eMail: fangzhongxue120@163.com
Dongling Zhang

^aSchool of Chemistry and Environmental Engineering, Yancheng Teachers University, Yancheng224007, P. R. of China eMail: fangzhongxue120@163.com
Kaining Zhang

^bCollege of Chemistry, Chemical Engineering and Materials Science, Shandong Normal University, Jinan 250014, P. R. of China eMail: liuzhenhua2012@163.com
Zhenhua Liu∗

^bCollege of Chemistry, Chemical Engineering and Materials Science, Shandong Normal University, Jinan 250014, P. R. of China eMail: liuzhenhua2012@163.com
Jing Lin

^aSchool of Chemistry and Environmental Engineering, Yancheng Teachers University, Yancheng224007, P. R. of China eMail: fangzhongxue120@163.com
Wei Cao

^aSchool of Chemistry and Environmental Engineering, Yancheng Teachers University, Yancheng224007, P. R. of China eMail: fangzhongxue120@163.com
Zhongxue Fang ∗

^aSchool of Chemistry and Environmental Engineering, Yancheng Teachers University, Yancheng224007, P. R. of China eMail: fangzhongxue120@163.com

Abstract

Alle Artikel dieser Rubrik

Abstract

An efficient approach for the amination of vinyl azides with N,N-dialkylacylamides has been developed. By using this protocol, structurally important α-ketoamides can be easily synthesized. The key to success is not only the introduction of a Cu(I)/oxygen catalytic system but also the utilization of t-BuOCl and benzoic acid as additives. The reaction is operationally simple, scalable, and displays broad scope and functional group tolerance. A possible mechanism involving copper-catalyzed oxidative generation of peroxide radicals is proposed.

Key words

amination - α-ketoamide - vinyl azide - copper-catalysis - N,N-dialkylacylamides

Volltext

Referenzen

References and Notes

For recent progress in the synthesis of vinyl azides, see:

1a Liu Z, Liu J, Zhang L, Liao P, Song J, Bi X. Angew. Chem. Int. Ed. 2014; 53: 5305
1b Liu Z, Liao P, Bi X. Org. Lett. 2014; 16: 3668

2a Lopez E, Lopez L. Angew. Chem. Int. Ed. 2017; 56: 5121
2b Shu W, Lorente A, Gómez-Bengoa E, Nevado C. Nat. Commun. 2017; 8: 13832
2c Wang Y.-F, Toh KK, Ng EP. J, Chiba S. J. Am. Chem. Soc. 2011; 133: 6411
2d Wang Y.-F, Chiba S. J. Am. Chem. Soc. 2009; 131: 12570
2e Wang Y.-F, Toh KK, Lee J.-Y, Chiba S. Angew. Chem. Int. Ed. 2011; 50: 5927

3a Lin C, Shen Y, Huang B, Liu Y, Cui S. J. Org. Chem. 2017; 82: 3950
3b Zhang Z, Kumar RK, Li G, Wu D, Bi X. Org. Lett. 2015; 17: 6190
3c Zhang F.-L, Wang Y.-F, Lonca GH, Zhu X, Chiba S. Angew. Chem. Int. Ed. 2014; 53: 4390
3d Qin C, Feng P, Ou Y, Shen T, Wang T, Jiao N. Angew. Chem. Int. Ed. 2013; 52: 7850

4a Qin H.-T, Wu S.-W, Liu J.-L, Liu F. Chem. Commun. 2017; 53: 1696
4b Chen W, Liu X, Chen E, Chen B, Shao J, Yu Y. Org. Chem. Front. 2017; 4: 1162

5a Xu H.-D, Zhou H, Pan Y.-P, Ren X.-T, Wu H, Han M, Han R.-Z, Shen M.-H. Angew. Chem. Int. Ed. 2016; 55: 2540
5b Farney EP, Yoon TP. Angew. Chem. Int. Ed. 2014; 53: 793

6 Wu S.-W, Liu F. Org. Lett. 2016; 18: 3642
7 Wang Y.-F, Lonca GH, Chiba S. Angew. Chem. Int. Ed. 2014; 53: 1067
8 Ning Y, Zhao X.-F, Wu Y.-B, Bi X. Org. Lett. 2017; 19: 6240

9a Wang Y, Wei C, Tang R, Zhan H, Lin J, Liu Z, Tao W, Fang Z. Org. Biomol. Chem. 2018; 16: 6191
9b Fang Z, Feng Y, Dong H, Li D, Tang T. Chem. Commun. 2016; 52: 11120
9c Liu J, Fang Z, Zhang Q, Liu Q, Bi X. Angew. Chem. Int. Ed. 2013; 125: 7091
9d Fang Z, Yuan H, Liu Y, Tong Z, Li H, Yang J, Barry B.-D, Liu J, Liao P, Zhang J, Liu Q, Bi X. Chem. Commun. 2012; 48: 8802
9e Wang K, Bi X, Xing S, Liao P, Fang Z, Meng X, Zhang Q, Liu Q, Ji Y. Green Chem. 2011; 13: 562

10a Blackburn EA, Walkinshaw MD. Curr. Opin. Pharmacol. 2011; 11: 365
10b Álvarez S, Álvarez R, Khanwalkar H, Germain P, Lemaire G, Rodríguez-Barrios F, Gronemeyer H, de Lera AR. Bioorg. Med. Chem. 2009; 17: 4345
10c Avolio S, Robertson K, Hernando JI. M, DiMuzio J, Summa V. Bioorg. Med. Chem. Lett. 2009; 19: 2295
10d Knust H, Nettekoven M, Pinard E, Roche O, Rogers-Evans M. PCT Int. Appl. WO 2009016087, 2009
10e Njoroge F, Chen KX, Shih N.-Y, Piwinski JJ. Acc. Chem. Res. 2008; 41: 50
10f De Clercq E. Nat. Rev. Drug Discovery 2007; 6: 1001

11 Liang S, Zeng C.-C, Tian H.-Y, Sun B.-G, Luo X.-G, Ren F.-Z. J. Org. Chem. 2016; 81: 11565

12a Hayashi H, Kaga A, Chiba S. J. Org. Chem. 2017; 82: 11981
12b Liu H, Feng M, Jiang X. Chem. Asian J. 2014; 9: 3360
12c Ding S, Jiao N. Angew. Chem. Int. Ed. 2012; 51: 9226
12d Liu Z.-Q, Zhao L, Shang X, Cui Z. Org. Lett. 2012; 14: 3218
12e Rolff M, Schottenheim J, Decker H, Tuczek F. Chem. Soc. Rev. 2011; 40: 4077
12f Too PC, Chua SH, Wong SH, Chiba S. J. Org. Chem. 2011; 76: 6159
12g Chiba S, Zhang L, Ang GY, Hui BW.-Q. Org. Lett. 2010; 12: 2052
12h Que LJ, Tolman WB. Nature 2008; 455: 333
12i Cramer CJ, Tolman WB. Acc. Chem. Res. 2007; 40: 601
12j Arends I, Gamez P, Sheldon RA. Adv. Inorg. Chem. 2006; 58: 235
12k Mirica LM, Vance M, Rudd DJ, Hedman B, Hodgson KO, Solomon EI, Stack TD. P. Science 2005; 308: 1890
12l Prigge ST, Eipper BA, Mains RE, Amzel LM. Science 2004; 304: 864
12m Wang Y, DuBios JL, Hedman B, Hodgson KO, Stack TD. P. Science 1998; 279: 537
12n Manis PA, Rathke MW. J. Org. Chem. 1980; 45: 4952

13 Fu J, Zanoni G, Anderson EA, Bi X. Chem. Soc. Rev. 2017; 46: 7208
14 Synthesis of 4a; Typical Procedure: To a solution of α-azido styrene (1a; 72.5 mg, 0.5 mmol), tert-butyl hypochlorite (113.1 μL, 1.0 mmol), and benzoic acid (122.1 mg, 1.0 mmol) in N,N-diethylformamide (2b; 1 mL) at room temperature, CuI (28.6 mg, 0.15 mmol) was added. The reaction mixture was heated at 100 °C and stirred for 5 h under an oxygen atmosphere, when TLC analysis confirmed that substrate 1a had been consumed. The resulting reaction mixture was cooled to room temperature and K₂CO₃ was added. The mixture was extracted with dichloromethane (3 × 15 mL), and the combined organic extracts were washed with brine (3 × 40 mL), dried over MgSO₄, filtered and concentrated. Purification of the crude product by flash column chromatography (silica gel; petroleum ether) afforded 4a (77% yield) as a yellow oil. N,N-Diethyl-2-oxo-2-phenylacetamide (4a): ¹H NMR (400 MHz, CDCl₃): δ = 7.93 (d, J = 7.1 Hz, 2 H), 7.64 (t, J = 7.4 Hz, 1 H), 7.51 (t, J = 7.7 Hz, 2 H), 3.61–3.53 (m, 2 H), 3.29–3.20 (m, 2 H), 1.29 (t, J = 7.2 Hz, 3 H), 1.16 (t, J = 7.1 Hz, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 191.5, 166.7, 134.5, 133.2, 129.6, 128.9, 42.0, 38.7, 14.0, 12.8. HRMS (ESI): m/z [M + H]⁺ calcd for C₁₂H₁₅NO₂: 206.1181; found: 206.1142.