Synlett 2019; 30(20): 2295-2299
DOI: 10.1055/s-0039-1691489
letter
© Georg Thieme Verlag Stuttgart · New York

Selectfluor-Mediated Tandem Cyclization of Enaminones for the Synthesis of 3-Fluorochromones

Venu Kandula
a  Chemistry Services, GVK Biosciences Pvt. Ltd., Survey Nos: 125 (part) & 126, IDA Mallapur, Hyderabad-500076, Telangana, India
b  Department of Chemistry, Koneru Laksmaiah Education Foundation, Vaddeswaram, Tadepalli, Guntur, Andhra Pradesh, 522502, India   Email: Manoranjan.behera@gvkbio.com
,
Pradeep Kumar Thota
a  Chemistry Services, GVK Biosciences Pvt. Ltd., Survey Nos: 125 (part) & 126, IDA Mallapur, Hyderabad-500076, Telangana, India
,
Poosa Mallesham
a  Chemistry Services, GVK Biosciences Pvt. Ltd., Survey Nos: 125 (part) & 126, IDA Mallapur, Hyderabad-500076, Telangana, India
,
K. Raghavulu
a  Chemistry Services, GVK Biosciences Pvt. Ltd., Survey Nos: 125 (part) & 126, IDA Mallapur, Hyderabad-500076, Telangana, India
,
Anindita Chatterjee
b  Department of Chemistry, Koneru Laksmaiah Education Foundation, Vaddeswaram, Tadepalli, Guntur, Andhra Pradesh, 522502, India   Email: Manoranjan.behera@gvkbio.com
,
Satyanarayana Yennam
a  Chemistry Services, GVK Biosciences Pvt. Ltd., Survey Nos: 125 (part) & 126, IDA Mallapur, Hyderabad-500076, Telangana, India
,
Manoranjan Behera
a  Chemistry Services, GVK Biosciences Pvt. Ltd., Survey Nos: 125 (part) & 126, IDA Mallapur, Hyderabad-500076, Telangana, India
› Author Affiliations
Further Information

Publication History

Received: 24 September 2019

Accepted after revision: 02 November 2019

Publication Date:
20 November 2019 (online)

Abstract

An efficient synthesis of various 3-fluorochromones (3-fluoro-4H-chromene-4-ones) from enamino ketones by using Selectfluor is described. The key step in the synthesis involves tandem fluorination and cyclization to form 3-fluorochromones in good yields. The significant features of this method include simple operational procedures, a high purity of the product, and excellent regioselectivity.

Supporting Information

 
  • References and Notes

  • 1 Reis J, Gaspar A, Milhazes N, Borges F. J. Med. Chem. 2017; 60: 7941
  • 2 Leahy JJ. J, Golding BT, Griffin RJ, Hardcastle IR, Richardson C, Rigoreau L, Smith GC. M. Bioorg. Med. Chem. Lett. 2004; 14: 6083
  • 3 Griffin RJ, Fontana G, Golding BT, Guiard S, Hardcastle IR, Leahy JJ. J, Martin N, Richardson L, Rigoreau M, Stockley GC. M, Smith C. J. Med. Chem. 2005; 48: 569
  • 4 Kim HP, Son KH, Chang HW, Kang SS. J. Pharmacol. Sci. (Amsterdam, Neth.) 2004; 96: 229
  • 5 Bhat AS, Whetstone JL, Brueggemeier RW. Tetrahedron Lett. 1999; 40: 2469
    • 6a Bennett CJ, Caldwell ST, McPhail DB, Morrice PC, Duthie GG, Hartley RC. Bioorg. Med. Chem. 2004; 12: 2079
    • 6b Krishnamachari V, Levin LH, Zhou C, Paré PW. Chem. Res. Toxicol. 2004; 17: 795
  • 7 Marder M, Viola H, Bacigaluppo JA, Colombo MI, Wasowski C, Wolfman C, Medina JH, Rúveda EA, Paladini AC. Biochem. Biophys. Res. Commun. 1998; 249: 481
  • 8 Hoult JR. S, Moroney MA, Payá M. Methods Enzymol. 1994; 234: 443
  • 9 Parmar VS, Bracke ME, Philippe J, Wengel J, Jain SC, Olsen CE, Bisht KS, Sharma NK, Courtens A, Sharma SK, Vennekens K, Van Marck V, Singh SK, Kumar N, Kumar A, Malhotra S, Kumar R, Rajwansh VK, Jain R, Mareel MM. Bioorg. Med. Chem. 1997; 5: 1609
  • 10 Galietta LJ. V, Springsteel MF, Eda M, Neidzinsk EJ, By K, Haddadin MJ, Kurth MJ, Nantz MH, Verkman AS. J. Biol. Chem. 2001; 276: 19723
    • 11a Horton DA, Bourne GT, Smythe ML. Chem. Rev. 2003; 103: 893
    • 11b Gaspar A, Matos JM, Garrido J, Uriarte E, Borges F. Chem. Rev. 2014; 114: 4960
  • 12 Lewinsohn E, Britsch L, Mazur Y, Gressel J. Plant Physiol. 1989; 91: 1323
    • 13a Kirk KL. Org. Process Res. Dev. 2008; 12: 305
    • 13b Smart BE. J. Fluorine Chem. 2001; 109: 3
    • 13c Thomas CJ. Curr. Top. Med. Chem. 2006; 6: 1529
  • 14 Müller K, Faeh C, Diederich F. Science 2007; 317: 1881
  • 15 Miller PW, Long NJ, Vilar R, Gee AD. Angew. Chem. Int. Ed. 2008; 47: 8998
    • 16a Dolensky B, Kirk KL. J. Org. Chem. 2001; 66: 4687
    • 16b Kirk KL. Curr. Top. Med. Chem. 2006; 6: 1447
    • 16c Saloutin VI, Skryabina ZE, Bazyl IT, Chupakhin ON. J. Fluorine Chem. 1993; 65: 37
    • 16d Kirk KL. J. Fluorine Chem. 2006; 127: 1013
  • 17 Fluorinated Heterocycles: ACS Symp. Ser. 1003 . Gakh AA, Kirk KL. American Chemical Society; Washington DC: 2009
  • 18 Zhao Q, Xiang H, Xiao J.-A, Xia P.-J, Wang J.-J, Chen X, Yang H. J. Org. Chem. 2017; 82: 9837
  • 19 Li N.-G, Shi Z.-H, Tang Y.-P, Ma H.-Y, Yang J.-P, Li B.-Q, Wang Z.-J, Song S.-L, Duan J.-A. J. Heterocycl. Chem. 2010; 47: 785
  • 20 Wang R, Han J, Li C, Zhang J, Liang Y, Wang T, Zhang Z. Org. Biomol. Chem. 2018; 16: 2479
  • 21 Betageri R, Zhang Y, Zindell RM, Kuzmich D, Kirrane TM, Bentzien J, Cardozo M, Capolino AJ, Fadra TN, Nelson RM, Zofia P, Shih D.-T, Shih C.-K, Zuvela-Jelaska L, Nabozny G, Thomson DS. Bioorg. Med. Chem. Lett. 2005; 15: 4761
  • 22 Bolós J, Gubert S, Anglada L, Planas JM, Burgarolas C, Castelló JM, Sacristán A, Ortiz JA. J. Med. Chem. 1996; 39: 2962
  • 23 Menichincheri M, Ballinari D, Bargiotti A, Bonomini L, Ceccarelli W, D’Alessio R, Fretta A, Moll J, Polucci P, Soncini C, Tibolla M, Trosset J.-Y, Vanotti E. J. Med. Chem. 2004; 47: 6466
  • 24 Médebielle M, Keirouz R, Okada E, Shibata D, Dolbier WR. Tetrahedron Lett. 2008; 49: 589
  • 25 Hou Y, Higashiya S, Fuchigami T. J. Org. Chem. 1999; 64: 3346
  • 26 Rozen S, Shaffer A. Org. Lett. 2017; 19: 4707
  • 27 Vints I, Rozen S. J. Org. Chem. 2014; 79: 7261
  • 28 Xu J, Kuang Z, Song Q. Chin. Chem. Lett. 2018; 29: 963
    • 29a Balakrishna C, Gudipati R, Kandula V, Satyanarayana Y, Uma Devi P, Behera M. New J. Chem. 2019; 43: 2458
    • 29b Balakrishna C, Kandula V, Gudipati R, Satyanarayana Y, Uma Devi P, Behera M. Synlett 2018; 29: 1087
    • 29c Sambaiah M, Raghavulu K, Kumar KS, Yennam S, Behera M. New J. Chem. 2017; 41: 10020
    • 29d Balakrishna C, Nagaraju P, Satyanarayana Y, Uma Devi P, Behera M. Bioorg. Med. Chem. Lett. 2015; 25: 4753
    • 29e Ravi KP, Behera M, Raghavulu K, Jaya Shree A, Yennam S. Tetrahedron Lett. 2012; 53: 4108
    • 29f Kandula V, Gudipati R, Chatterjee A, Kaliyaperumala M, Yennam S, Behera M. J. Chem. Sci. (Berlin, Ger.) 2017; 129: 1233
  • 30 Nyffeler PT, Gonzalez Durón S, Burkart MD, Vincent SP, Wong C.-H. Angew. Chem. Int. Ed. 2005; 44: 192
  • 31 Harel D, Khalid SA, Kaiser M, Brun R, Wünsch B, Schmidt TJ. J. Ethnopharmacol. 2011; 137: 620
  • 32 3-Fluoro-4H-chromen-4-one (3a); Typical Procedure Selectfluor (708 mg, 2 mmol) was added to a stirred solution of enaminone 2a (191 mg, 1 mmol) in DCE (5 mL) at 0 °C, and the mixture (a white suspension) was stirred at r.t. for 24 h. When the reaction was complete (TLC, 30% EtOAc–PE), the mixture was poured into ice-cold water and stirred for 10 min. The mixture was then extracted with EtOAc (3 ×) and the combined organic layers were washed with water and brine, then dried (Na2SO4), filtered, and concentrated. The resulting crude product was purified by flash column chromatography [silica gel (100–200 mesh), 15–20% EtOAc–PE] to give an off-white solid; yield:135 mg (82%); mp 158–162 °C. IR (KBr): 3084, 2967, 1814, 1709, 1587, 1483, 1395, 1194, 955, 753 cm–1. 1H NMR (500 MHz, DMSO-d 6): δ = 8.96 (d, J = 4 Hz, 1 H), 8.16 (d, J = 8 Hz, 1 H), 7.87 (t, J = 8.5 Hz, 1 H), 7.75 (d, J = 8.5 Hz, 1 H), 7.55 (t, J = 7.5 Hz, 1 H). 13C NMR (125 MHz, DMSO-d 6): δ = 169.4 (d, J = 15.5 Hz), 155.3, 149.6 (d, J = 242.2 Hz), 147.7, 145.1 (d, J = 40.6 Hz), 134.5, 125.5, 124.2, 118.7. 19F NMR (470 MHz, CDCl3): δ = –165.7. MS (EI): m/z (%) = 165 [M + 1]+ (100).