Treatment of Olefinic Amides with NBS in Water: Synthesis of Monobromo- and Multibromobenzoxazines

Abstract

Treatment of olefinic amides with N-bromosuccinimide (NBS) in water is reported. Monobromobenzoxazines were mainly formed at room temperature, while at 80 °C multibromobenzoxazines were preferentially generated. Mechanism studies showed that the reaction might proceed via a cascade of electrophilic addition at the C=C bond followed by electrophilic substitution at the aromatic ring. No additives are required in this protocol.

Key words

benzoxazines - water - metal free - bromination - selectivity

• References

• 1a Krantz A, Spencer RW, Tam TF, Liak TJ, Copp LJ, Thomas EM, Rafferty SP. J. Med. Chem. 1990; 33: 464
• 1b Hays SJ, Caprathe BW, Gilmore JL, Amin N, Emmerling MR, Michael W, Nadimpalli R, Nath R, Raser KJ, Stafford D, Watson D, Wang K, Jaen JC. J. Med. Chem. 1998; 41: 1060
• 1c Zhang P.-W, Terefenko TA, Fensome A, Zhang Z.-M, Zhu Y, Cohen J, Winneker R, Wrobel J, Yardley J. Bioorg. Med. Chem. Lett. 2002; 12: 787
• 2a Djabrouhou N, Guermouche MH. J. Pharm. Biomed. Anal. 2014; 100: 11
• 2b Zhang P, Terefenko TA, Fensome A, Wrobel J, Winneker R, Lundeen S, Marschke KB, Zhang Z. J. Med. Chem. 2002; 45: 4379
• 3a Wang Z, Ran Q.-C, Zhu R.-Q, Gu Y. RSC Adv. 2013; 3: 1350
• 3b Wang H, Wang J, He X.-Y, Feng T.-T, Ramdani N, Luan M.-J, Liu W.-B, Xu X.-D. RSC Adv. 2014; 4: 64798

Recent examples, see:
• 4a Lee W.-C, Shen H.-C, Hu W.-P, Lo W.-S, Murali C, Vandavasi JK, Wang J.-J. Adv. Synth. Catal. 2012; 354: 2218
• 4b Liu Q.-L, Chen P.-H, Liu G.-S. ACS Catal. 2013; 3: 178
• 4c Reddy BV. S, Babu RA, Reddy MR, Reddy BJ. M, Sridhar B. RSC Adv. 2014; 4: 44629
• 4d Munusamy S, Venkatesan S, Sathiyanarayanan KI. Tetrahedron Lett. 2015; 56: 203
• 5a Okuma K, Yasuda T, Takeshita I, Shioji K, Yokomori Y. Tetrahedron 2007; 63: 8250
• 5b Jaganathan A, Garzan A, Whitehead DC, Staples RJ, Borhan B. Angew. Chem. Int. Ed. 2011; 50: 2593
• 5c Cahard E, Bremeyer N, Gaunt MJ. Angew. Chem. Int. Ed. 2013; 52: 9284
• 5d Yin Q, You S.-L. Org. Lett. 2014; 16: 2426
• 5e Deng Q.-H, Chen J.-R, Wei Q, Zhao Q.-Q, Lu L.-Q, Xiao W.-J. Chem. Commun. 2015; 51: 3537
• 6 Li B, Park Y, Chang S. J. Am. Chem. Soc. 2014; 136: 1125
• 7a Kobayashi K, Miyamoto K, Morikaea O, Konishi H. Bull. Chem. Soc. Jpn. 2005; 78: 886
• 7b Yu Y.-J, Zhang F.-L, Cheng J, Hei J.-H, Deng W.-T, Wang Y.-F. Org. Lett. 2018; 20: 24
• 7c Cortés González MA, Nordeman P, Gómez AB, Meyer DN, Antoni G, Schou M, Szabó KJ. Chem. Commun. 2018; 54: 4286
• 8 Okuma K, Yasuda T, Takeshita I, Shioji K, Yokomori Y. Bull. Chem. Soc. Jpn. 2007; 80: 1824
• 9a Wang Y.-M, Wu J, Hoong C, Rauniyar V, Toste FD. J. Am. Chem. Soc. 2012; 134: 12928
• 9b Zhao J.-F, Duan X.-H, Yang H, Guo L.-N. J. Org. Chem. 2015; 80: 11149
• 10 Fu W.-J, Han X, Zhu M, Xu C, Wang Z.-Q, Ji B.-M, Hao X.-Q, Song M.-P. Chem. Commun. 2016; 52: 13413
• 11 Yang H, Duan X.-H, Zhao J.-F, Guo L.-N. Org. Lett. 2015; 17: 1998
• 12 Wang J, Sang R.-Y, Chong X.-L, Zhao Y.-N, Fan W.-J, Li Z.-J, Zhao J.-C. Chem. Commun. 2017; 53: 7961
• 13a Chu X.-Q, Xu X.-P, Meng H, Ji S.-J. RSC Adv. 2015; 5: 67829
• 13b Zhu S.-L, Ji S.-J, Zhang Y. Tetrahedron 2007; 63: 9365
• 13c Jiang R, Wu X.-J, Zhu X, Xu X.-P, Ji S.-J. Eur. J. Org. Chem. 2010; 5946
• 13d Jiang R, Xu H.-Y, Xu X.-P, Chu X.-Q, Ji S.-J. Org. Biomol. Chem. 2011; 9: 5659
• 14 Filler R. Chem. Rev. 1963; 63: 21

Recent examples, see:
• 15a Chun S, Chung YK. Org. Lett. 2018; 20: 5583
• 15b Zhou J, Yeung Y.-Y. Org. Biomol. Chem. 2014; 12: 7482
• 15c Zhou L, Tan CK, Jiang X.-J, Chen F, Yeung Y.-Y. J. Am. Chem. Soc. 2010; 132: 15474
• 15d Yu WZ, Chen F, Cheng YA, Yeung Y.-Y. J. Org. Chem. 2015; 80: 2815
• 15e Chen J, Chng S, Zhou L, Yeung Y.-Y. Org. Lett. 2011; 13: 6456
• 16a Ross SD, Finkelstein M, Petersen RC. J. Am. Chem. Soc. 1958; 80: 4327
• 16b Ni S, El Remaily MA. E. A. A. A, Franzén J. Adv. Synth. Catal. 2018; 360: 4197
• 16c Shibatomi K, Zhang Y, Yamamoto H. Chem. Asian J. 2008; 3: 1581
• 17a Saikia I, Borah AJ, Phukan P. Chem. Rev. 2016; 116: 6837
• 17b Huang Z, Zhan M, Zhang S.-G, Luo Q, Zhang W.-Z, Xi Z.-F. Org. Chem. Front. 2017; 4: 1785
• 18a Lindström UM. Chem. Rev. 2002; 102: 2751
• 18b Kobayashi S, Manabe K. Acc. Chem. Res. 2002; 35: 209
• 18c Breslow R. Acc. Chem. Res. 2004; 37: 471
• 18d Li C.-J, Chen L. Chem. Soc. Rev. 2006; 35: 68
• 18e Chen L, Li C.-J. Adv. Synth. Catal. 2006; 348: 1459
• 18f Chanda A, Fokin VV. Chem. Rev. 2009; 109: 725
• 18g Butler RN, Coyne AG. Chem. Rev. 2010; 110: 6302
• 18h Gawande MB, Bonifacio VD. B, Luque R, Branco PS, Varma RS. Chem. Soc. Rev. 2013; 42: 5522
• 19a Copley SD, Knowles JR. J. Am. Chem. Soc. 1987; 109: 5008
• 19b Breslow R, Maitra U, Rideout D. Tetrahedron Lett. 1983; 24: 1901
• 20a Xie P.-Z, Wang J.-Y, Liu Y.-N, Fan J, Wo X.-Y, Fu W.-S, Sun Z.-L, Loh T.-P. Nat. Commun. 2018; 9: 1321
• 20b Wang B, Tang L, Liu L.-Y, Li Y.-N, Yang Y, Wang Z.-Y. Green Chem. 2017; 19: 5794
• 21 When R² = H, only N-(2-(2-bromoacetyl)phenyl)benzamide could be obtained, and when we employed the corresponding alkynyl amide, the reaction gave N-(2-(2,2-dibromoacetyl)phenyl)benzamide as product (Scheme 8).
• 22 See Supporting Information, Figure S2.
• 23a Zhang M.-Z, Sheng W.-B, Jiang Q, Tian M, Yin Y, Guo C.-C. J. Org. Chem. 2014; 79: 10829
• 23b Podgorsek A, Stavber S, Zupan M, Iskra J. Tetrahedron 2009; 65: 4429