Citation: Zhang Xiaoxiang, Lü Chang, Li Ping, Yong Wanxiong, Li Jing, Zhu Xinbao. Rapid Access to 4H-3, 1-Benzoxazin-4-ones via Gold-Catalyzed One-Pot Oxidative Rearrangement of 2-Alkynyl Arylazides[J]. Chinese Journal of Organic Chemistry, ;2018, 38(1): 208-214. doi: 10.6023/cjoc201706030 shu

Rapid Access to 4H-3, 1-Benzoxazin-4-ones via Gold-Catalyzed One-Pot Oxidative Rearrangement of 2-Alkynyl Arylazides

Jiangsu Key Laboratory of Biomass-based Green Fuels and Chemicals, College of Chemical Engineering, Nanjing Forestry University, Nanjing 210037

Corresponding author: Zhang Xiaoxiang, zhangxiaoxiang@njfu.edu.cn Zhu Xinbao, zhuxinbao@njfu.com.cn
Received Date: 23 June 2017
Revised Date: 17 August 2017
Available Online: 15 January 2017
Fund Project: Young Natural Science Foundation of Jiangsu Province BK20130962the Young National Natural Science Foundation of China 21302096Postgraduate Research & Practice Innovation Program of Jiangsu Province KYLX16_0844Young Natural Science Foundation of Jiangsu Province BK20171449Project supported by the Project supported by the Young National Natural Science Foundation of China (No. 21302096), the Young Natural Science Foundation of Jiangsu Province (Nos. BK20171449, BK20130962), the Postgraduate Research & Practice Innovation Program of Jiangsu Province (No. KYLX16_0844), and the Project Fund from the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD)

Figures(3)

The one-pot one-step synthetic method of 4H-3, 1-benzoxazin-4-ones via the gold-catalyzed oxidative rearrangement of 2-alkynyl arylazides has been developed. The desired products were obtained in moderate to excellent yields under mild reaction conditions. In most cases, using acetic acid as solvent the reactions were shown to proceed very fast within 1 h.
- gold-catalyzed,
- oxidative rearrangement,
- one-pot,
- 2-alkynyl arylazides
1. [1]
  (a) Padwal, R. Curr. Opin. Invest. Drugs 2008, 9, 414.
  (b) Eissa, A. M. F. ; El-Sayed, R. J. Heterocycl. Chem. 2006, 43, 1.
  (c) Neumann, U. ; Schechter, N. M. ; Gutschow, M. Bioorg. Med. Chem. 2001, 9, 947.
  (d) Gutschow, M. ; Neumann, U. Bioorg. Med. Chem. 1997, 5, 1935.
  (e) Krantz, A. ; Spencer, R. W. ; Tam, T. F. ; Liak, T. J. ; Copp, L. J. ; Thomas, E. M. ; Raﬀerty, S. P. J. Med. Chem. 1990, 33, 464.
2. [2]
  (a) Krantz, A. ; Spencer, R. W. ; Tam, T. F. ; Liak, T. J. ; Copp, L. J. ; Thomas, E. M. ; Rafferty, S. P. J. Med. Chem. 1990, 33, 464.
  (b) Stein, R. L. ; Strimpler, A. M. ; Viscarello, B. R. ; Wildonger, R. A. ; Mauger, R. C. ; Trainor, D. A. Biochemistry 1987, 26, 4126.
3. [3]
  For some examples, see: (a) Yamada, Y. ; Kato, T. ; Ogino, H. ; Ashina, S. ; Kato, K. Horm. Metab. Res. 2008, 40, 539.
  (b) Padwal, R. Curr. Opin. Invest. Drugs 2008, 9, 414.
4. [4]
  Hedstrom, L.; Moorman, A. R.; Dobbs, J.; Abeles, R. H. Biochemistry 1984, 23, 1753. doi: 10.1021/bi00303a026
5. [5]
  Jarvest, R. L.; Parratt, M. J.; Debouck, C. M.; Gorniak, J. G.; Jennings, L. J.; Serafinowska, H. T.; Strickler, J. E. Bioorg. Med. Chem. Lett. 1996, 6, 2463. doi: 10.1016/0960-894X(96)00455-6
6. [6]
  (a) Li, W. F. ; Wu, X. F. J. Org. Chem. 2014, 79, 10410.
  (b) Yamashita, M. ; Iida, A. Tetrahedron Lett. 2014, 55, 2991.
  (c) Lian, X. L. ; Lei, H. ; Quan, X. J. ; Ren, Z. H. ; Wang, Y. Y. ; . Guan, Z. H. Chem. Commun. 2013, 49, 8196.
  (d) Ge, Z. Y. ; Xu, Q. M. ; Fei, X. D. ; Tang, T. ; Zhu, Y. M. ; Ji, S. J. J. Org. Chem. 2013, 78, 4524.
  (e) Xie, Y. Y. ; Wang, S. P. J. Chem. Res. 2012, 36, 123.
  (f) Wu X. F. ; Neumann, H. ; Beller, M. Chem. Eur. J. 2012, 18, 12599.
  (g) Kumar, R. A. ; Maheswari, C. U. ; Ghantasala, S. ; Jyothi, C. ; Reddy, K. R. Adv. Synth. Catal. 2011, 353, 401.
  (h) Xue, S. ; McKenna, J. ; Shieh, W. C. ; Repic, O. J. Org. Chem. 2004, 69, 6474.
  (i) Chenard, B. L. ; Welch, W. M. ; Blake, J. F. ; Butler, T. W. ; Reinhold, A. ; Ewing, F. E. ; Menniti, F. S. ; Pagnozzi, M. J. J. Med. Chem. 2001, 44, 1710.
  (j) Coppola, G. M. J. Heterocycl. Chem. 1999, 36, 563.
  (k) Larksarp, C. ; Alper, H. Org. Lett. 1999, 1, 1619.
  (l) Kotsuki, H. ; Sakai, H. ; Morimoto, H. ; Suenaga, H. Synlett 1999, 1993.
  (m) Cacchi, S. ; Fabrizi, G. ; Marinelli, F. Synlett 1996, 997.
  (n) Larock, R. C; . Fellows, C. A. J. Org. Chem. 1980, 45, 363.
  (o) Errede, L. A. J. Org. Chem. 1976, 41, 1763.
  (p) Jackson, T. G. ; Morris, S. R. ; Turner, R. H. J. Chem. Soc. 1968, 13, 1592.
  (q) Taylor, E. C. ; Knopf, R. I. ; Borror, A. L. J. Am. Chem. Soc. 1960, 82, 3152.
7. [7]
  For recent examples on the synthesis of 4H-3, 1-benzoxazin-4-ones 3, see: (a) Wang, L. ; Xie, Y. -B; Huang, N. -Y. ; Yan, J. -Y. ; Hu, W. -M. ; Liu, M. -G. ; Ding, M. -W. ACS Catal. 2016, 6, 4010.
  (b) Verma, A. ; Kumar, S. Org. Lett. 2016, 18, 4388.
  (c) Arcadi, A. ; Chiarini, M. ; Vecchio, L. D. ; Marinelli, F. ; Michelet, V. Chem. Commun. 2016, 52, 1458.
  (d) Laha, J. K. ; Patel, K. V. ; Tummalapalli, K. S. S. ; Dayal, N. Chem. Commun. 2016, 52, 10245.
  (e) Prakash, R. ; Gogoi, S. Adv. Synth. Catal. 2016, 19, 3046.
  (f) Yu, J. ; Zhang-Negrerie, D. ; Du, Y. Eur. J. Org. Chem. 2016, 2016, 562.
  (g) Wu, X. F. ; Schranck, J. ; Neumann, H. ; Beller, M. Chem. -Eur. J. 2011, 17, 12246.
  (h) Liu, Q. ; Chen, P. ; Liu, G. ACS Catal. 2013, 3, 178.
  (i) Li, W. ; Wu, X. F. J. Org. Chem. 2014, 79, 10410.
  (j) Chavan, S. P. ; Bhanage, B. M. Eur. J. Org. Chem. 2015, 2015, 2405.
  (k) Munusamy, S. ; Venkatesan, S. ; Sathiyanarayanan, K. I. Tetrahedron Lett. 2015, 56, 203.
  (l) Larksarp, C. ; Alper, H. Org. Lett. 1999, 1, 1619.
  (m) Salvadori, J. ; Balducci, E. ; Zaza, S. ; Petricci, E. ; Taddei, M. J. Org. Chem. 2010, 75, 1841.
  (n) Nayak, M. K. ; Kim, B. H. ; Kwon, J. E. ; Park, S. ; Seo, J. ; Chung, J. W. ; Park, S. Y. Chem. -Eur. J. 2010, 16, 7437.
8. [8]
  For recent selected reviews on gold-catalyzed reactions, see: (a) Harris, R. J. ; Widenhoefer, R. A. Chem. Soc. Rev. 2016, 45, 4533.
  (b) Asiri, A. M. ; Hashmi, A. S. K. Chem. Soc. Rev. 2016, 45, 4471.
  (c) Zheng, Z. ; Wang, Z. ; Wang, Y. ; Zhang, L. Chem. Soc. Rev. 2016, 45, 4448.
  (d) Ziand, W. ; Toste, F. D. Chem. Soc. Rev. 2016, 45, 4567.
  (e) Huple, D. B. ; Ghorpade, S. ; Liu, R. -S. Adv. Synth. Catal. 2016, 358, 1348.
  (f) Dorel, R. ; Echavarren, A. M. Chem. Rev. 2015, 115, 9028.
  (g) Jia, M. ; Bandini, M. ACS Catal. 2015, 5, 1638.
  (h) Wang, Y. ; Muratore, M. E. ; Echavarren, A. M. Chem. Eur. J. 2015, 21, 7332.
  (i) Zhang, L. Acc. Chem. Res. 2014, 47, 877.
  (j) Yeom, H. -S. ; Shin, S. Acc. Chem. Res. 2014, 47, 966.
  (k) Fensterbank, L. ; Malacria, M. Acc. Chem. Res. 2014, 47, 953.
  (l) Benitez, D. ; Shapiro, N. D. ; Tkatchouk, E. ; Wang, Y. ; God-dard Ⅲ, W. A. ; Toste, F. D. Nat. Chem. 2009, 1, 482.
  (m) Hashmi, A. S. K. Chem. Rev. 2007, 107, 3180.
  (n) Wu, W. -T. ; Zhang, L. ; You, S. -L. Acta Chim. Sinica 2017, 75, 419(in Chinese). (吴文挺, 张立明, 化学学报, 2017, 75, 419. )
  for recent selected examples, see: (o) Zhao, J. -R. ; Yuan, X. ; Wang, Z. ; Chen, S. ; Zhang, Z. -X. ; Xue, W. Org. Chem. Front. 2015, 2, 34.
  (p) Li, L. ; Zhou, B. ; Ye, L. Chin. J. Org. Chem. 2015, 35, 655(in Chinese). (李龙, 周波, 叶龙武, 有机化学, 2015, 35, 655. )
  (q) Zhang, P. -C. ; Wang, Y. ; Qian, D. ; Li, W. ; Zhang, J. Chin. J. Chem. 2017, 35, 849.
9. [9]
  For recent selected a review on the generation of α-imino gold carbenes, see: Davies, P. W. ; Garz n, M. Asian J. Org. Chem. 2015, 4, 694.
10. [10]
  For recent selected examples, see: (a) Lonca, G. H. ; Tejo, C. ; Chan, H. L. ; Chiba, S. ; Gagosz, F. Chem. Commun. 2017, 53, 736.
  (b) Jin, H. ; Tian, B. ; Song, X. ; Xie, J. ; Rudolph, M. ; Rominger, F. ; Hashmi, A. S. K. Angew. Chem., Int. Ed. 2016, 55, 12688.
  (c) Pan, Y. ; Chen, G. -W. ; Shen, C. -H. ; He, W. ; Ye, L. -W. Org. Chem. Front. 2016, 3, 391.
  (d) Li, N. ; Lian, X. -L. ; Li, Y. -H. ; Wang, T. -Y. ; Han, Z. -Y. ; Zhang, L. ; Gong, L. -Z. Org. Lett. 2016, 18, 4178.
  (e) Jin, H. ; Huang, L. ; Xie, J. ; Rudolph, M. ; Rominger, F. ; Hashmi, A. S. K. Angew. Chem., Int. Ed. 2016, 55, 794.
  (f) Zhou, A. -H. ; He, Q. ; Shu, C. ; Yu, Y. -F. ; Liu, S. ; Zhao, T. ; Zhang, W. ; Lu, X. ; Ye, L. -W. Chem. Sci. 2015, 6, 1265.
  (g) Xiao, X. -Y. ; Zhou, A. -H. ; Shu, C. ; Pan, F. ; Li, T. ; Ye, L-W. Chem. -Asian J. 2015, 10, 1854.
  (h) Shen, C. -H. ; Pan, Y. ; Yu, Y. -F. ; Wang, Z. -S. ; He, W. ; Li, T. ; Ye, L. -W. J. Organomet. Chem. 2015, 795, 63.
  (i) Li, N. ; Wang, T. -Y. ; Gong, L. -Z; Zhang, L. Chem. -Eur. J. 2015, 21, 3585.
  (j) Shu, C. ; Wang, Y. -H. ; Zhou, B. ; Li, X. -L. ; Ping, Y. -F. ; Lu, X. ; Ye, L. -W. J. Am. Chem. Soc. 2015, 137, 9567.
  (k) Zhu, L. ; Yu, Y. ; Mao, Z. ; Huang, X. Org. Lett. 2015, 17, 30.
  (l) Wu, Y. ; Zhu, L. ; Yu, Y. ; Luo, X. ; Huang, X. J. Org. Chem. 2015, 80, 11407.
  (m) Pawar, S. K. ; Sahani, R. L. ; Liu, R. -S. Chem. -Eur. J. 2015, 21, 10843.
  (n) Prechter, A. ; Henrion, G. ; dit Bel, P. F. ; Gagosz, F. Angew. Chem., Int. Ed. 2014, 53, 4959.
  (o) Garzón M. ; Davies, P. W. Org. Lett. 2014, 16, 4850.
  (p) Tokimizu, Y. ; Oishi, S. ; Fujii, N. ; Ohno, H. Org. Lett. 2014, 16, 3138.
  (q) Chatzopoulou, E. ; Davies, P. W. Chem. Commun. 2013, 49, 8617.
  (r) Yan, Z. -Y. ; Xiao, Y. ; Zhang, L. Angew. Chem., Int. Ed. 2012, 51, 8624.
  (s) Xiao, Y. ; Zhang, L. Org. Lett. 2012, 14, 4662.
  (t) Lu, B. ; Luo, Y. ; Liu, L. ; Ye, L. ; Wang, Y. ; Zhang, L. Angew. Chem., Int. Ed. 2011, 50, 8358.
  (u) Wetzel, A. ; Gagosz, F. Angew. Chem., Int. Ed. 2011, 50, 7354.
  (v) Li, C. ; Zhang, L. Org. Lett. 2011, 13, 1738.
  (w) Davies, P. W. ; Cremones, A. ; Dumitrescu, L. Angew. Chem., Int. Ed. 2011, 50, 8931.
  (x) Gorin, D. J. ; Davis, N. R. ; Toste, F. D. J. Am. Chem. Soc. 2005, 127, 11260.
11. [11]
  For our recent studies on gold-catalyzed tandem reactions, see: (a) Chen, C. ; Zou, Y. ; Chen, X. ; Zhang, X. ; Rao, W. ; Chan, P. W. H. Org. Lett. 2016, 18, 4730.
  (b) Zhang, X. ; Sun, X. ; Fan, H. ; Lyu, C. ; Li, P. ; Zhang, H. ; Rao, W. RSC Adv. 2016, 6, 56319.
  (c) Zhang, X. ; Sun, X. ; Fan, H. ; Li, P. ; Lyu, C. ; Rao, W. Eur. J. Org. Chem. 2016, 25, 4265.
  (d) Zhang, X. ; Sun, X. ; Fan, H. ; Cui, X. ; Ma, M. Chin. J. Org. Chem. 2015, 35, 1469(in Chinese). (张小祥, 孙小萍, 张海飞, 崔杏丽, 马猛涛, 有机化学, 2015, 35, 1469. )
12. [12]
  Wang, J.; Jiang, X.; Zhang, Y.; Zhu, Y.; Shen, J. Tetrahedron Lett. 2015, 56, 2349. doi: 10.1016/j.tetlet.2015.03.121
13. [13]
  Eid, A. I. Eur. J. Med. Chem. 1979, 14, 463.
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