A Detour Route for meta Functionalization of Phenols

Abstract

Cyclohexadienones participate in a two-step procedure, a Michael addition followed by aromatization, providing hitherto difficult-to-synthesize meta-functionalized phenol derivatives in good yield. Application of the developed approach is exemplified by synthesizing C-aryl acetophenones, C-aryl glycines, and elemicin – an allylphenol natural product.

Key words

cyclohexadienones - aryl acetophenones - aryl glycines - aromatization - Michael addition

• References

• 1a Mishra BB, Tiwari VK. Eur. J. Med. Chem. 2011; 46: 4769
• 1b Khoddami A, Wilkes MA, Roberts TH. Molecules 2013; 18: 2328
• 1c Amorati R, Valgimigli L. Org. Biomol. Chem. 2012; 10: 4147
• 1d Pereira DM, Valentao P, Pereira JA, Andrade PB. Molecules 2009; 2202
• 1e Dimitrios B. Trends Food Sci. Technol. 2006; 17: 505
• 1f Fabricant DS, Farnsworth NR. Environ. Health Perspect. 2001; 109: 69
• 2a Friedel C, Crafts JM. J. Chem. Soc. 1877; 32: 725
• 2b Rueping M, Nachtsheim BJ. Beilstein J. Org. Chem. 2010; 6: No. 6
• 2c Duff JC, Bills EJ. J. Chem. Soc. 1932; 273: 1987
• 2d Ganem B. Angew. Chem., Int. Ed. Engl. 1996; 35: 936
• 3a Ackermann L, Diers E, Manvar A. Org. Lett. 2012; 14: 1154
• 3b Reddy MC, Jeganmohan M. Chem. Commun. 2013; 49: 481
• 3c Reddy MC, Jeganmohan M. Eur. J. Org. Chem. 2013; 1150
• 4a Jana R, Pathak TP, Sigman MS. Chem. Rev. 2011; 111: 1417
• 4b Shaughnessy KH. Metal-Catalyzed Reactions in Water . Dixneuf PH, Cadierno V. Wiley-VCH; Weinhein: 2013. 1st ed., 1-46
• 4c Metal-Catalyzed Cross-Coupling Reactions . de Meijere A, Diederich F. Wiley-VCH; Weinheim: 2004. 2nd ed
• 5 Phipps RJ, Gaunt MJ. Science 2009; 323: 1593
• 6a Chittimalla SK, Bandi C, Putturu S, Kuppusamy R, Boellaard KC, Tan DC. A, Lum DM. J. Eur. J. Org. Chem. 2014; 2565
• 6b Ye Y, Wang H, Fan R. Synlett 2011; 923
• 7a Wang L, Wang S.-E, Wang W, Fan R. RSC Adv. 2013; 3: 5775
• 7b Giroux M.-A, Guerard KC, Beaulieu M.-A, Sabot C, Canesi S. Eur. J. Org. Chem. 2009; 3871

For reviews on cyclohexadienones, see:
• 8a Pouysegu L, Deffieux D, Quideau S. Tetrahedron 2010; 66: 2235
• 8b Magdziak D, Meek SJ, Pettus TR. R. Chem. Rev. 2004; 104: 1383
• 8c Liao C.-C, Peddinti RK. Acc. Chem. Res. 2002; 35: 856

For the synthetic protocols for the preparation of cyclohexadienones, see:
• 8d Tamura Y, Yakura T, Haruta J, Kita Y. J. Org. Chem. 1987; 52: 3927
• 8e Lewis N, Wallbank P. Synthesis 1987; 1103
• 8f Chittimalla SK, Kuppusamy R, Chakrabarti A. Synlett 2012; 23: 1901
• 8g Chittimalla SK, Kuppusamy R, Thiayagarajan K, Bandi C. Eur. J. Org. Chem. 2013; 2715
• 8h Chittimalla SK, Bandi C. RSC Adv. 2013; 3: 13663
• 8i Chittimalla SK, Liao C.-C. Tetrahedron 2003; 59: 4039

For the preparation and analytical data for compound 1, see:
• 8j Deffieux D, Fabre I, Titz A, Leger J.-M, Quideau S. J. Org. Chem. 2004; 69: 8731

For compound 6, see:
• 8k Pelter A, Elgendy SM. A. J. Chem. Soc., Perkin Trans. 1 1993; 1891

For compound 7 and 8, see:
• 8l Camps P, González A, Muñoz-Torrero D, Simon M, Zúñiga A, Martins MA, Font-Bardia M, Solans X. Tetrahedron 2000; 56: 8141
• 8m For compound 10, see ref. 6.
• 9a Sun X, Qiu J. WO 2011038204 A1, 2011
• 9b Larsen RD, Reamer RA, Corley EG, Davis P, Grabowski EJ. J, Reider PJ, Shinkai I. J. Org. Chem. 1991; 56: 6034
• 9c Jain AC, Bambah PK. Indian J. Chem., Sect. B: Org. Chem. Incl. Med. Chem. 1987; 26: 628
• 9d Bhandari P, Crombie L, Daniels P, Holden I, Van Bruggen N, Whiting DA. J. Chem. Soc., Perkin Trans. 1 1992; 839
• 10a Jain N, Krishnamurty HG. Indian J. Chem., Sect. B: Org. Chem. Incl. Med. Chem. 2000; 39: 817
• 10b Latey PP, Deshpande VH. Indian J. Chem., Sect. B: Org. Chem. Incl. Med. Chem. 1986; 25: 299
• 10c Napolitano E, Fiaschi R, Marsili A. Gazz. Chim. Ital. 1988; 118: 415
• 10d Wu M, Sun Q, Yang C, Chen D, Ding J, Chen Y, Lin L, Xie Y. Bioorg. Med. Chem. Lett. 2007; 17: 869
• 11a Nicolaou KC, Boddy CN. C, Brase S, Winssinger N. Angew. Chem. Int. Ed. 1999; 38: 2096
• 11b Salituro GM, Townsend CA. J. Am. Chem. Soc. 1990; 112: 760
• 12a Williams RM, Hendrix JA. Chem. Rev. 1992; 92: 889
• 12b Wolter F, Schoof S, Süssmuth RD. Top. Curr. Chem. 2007; 267: 143
• 13 Hosomi A, Sakurai H. J. Am. Chem. Soc. 1977; 99: 1673
• 14 Shah G, Shri R, Panchal V, Sharma N, Singh B, Mann AS. J. Adv. Pharm. Technol. Res. 2011; 1: 3
• 15 Stetter H. Angew. Chem., Int. Ed. Engl. 1976; 15: 639
• 16 Sarkar SD, Grimme S, Studer A. J. Am. Chem. Soc. 2010; 132: 1190