Synthesis 2012; 44(14): 2115-2137
DOI: 10.1055/s-0031-1289770
review
© Georg Thieme Verlag Stuttgart · New York

Synthesis and Properties of Fluoropyrroles and Their Analogues

Olga V. Serdyuk
a   Southern Federal University, Department of Chemistry, Zorge 7, Rostov-on-Don, 344090, Russian Federation, Fax: +7(863)2975146   Email: oserduke@mail.ru
,
Vasiliy M. Muzalevskiy
b   Moscow State University, Department of Chemistry, Leninskie Gory, Moscow, 119992, Russian Federation , Email: nen@acylium.chem.msu.ru
,
Valentine G. Nenajdenko*
b   Moscow State University, Department of Chemistry, Leninskie Gory, Moscow, 119992, Russian Federation , Email: nen@acylium.chem.msu.ru
› Author Affiliations
Further Information

Publication History

Received: 26 March 2012

Accepted after revision: 20 April 2012

Publication Date:
19 June 2012 (online)


Abstract

Pyrroles and indoles are important subunits of many natural products and pharmacologically active compounds. Fluorinated compounds possess a unique complex of physical, chemical, and biological properties that results in their wide application as construction materials, liquid crystalline materials, agrochemicals, and drugs. The review covers the synthesis and properties of fluoropyrroles and their benzo analogues. The literature up to 2011 is highlighted.

1 Introduction

2 Synthesis of Fluoropyrroles

2.1 Functionalization of the Pyrrole Ring

2.2 Cycloaddition and Heterocyclization

2.3 Other Methods

3 Synthesis of Indoles, Indolizines and Deazopurines with Fluorinated Pyrrole Rings

3.1 Functionalization of the Pyrrole Ring

3.2 Heterocyclizations

4 Synthesis of Indoles with Fluorine Atoms on the Carbocycle

5 Properties of Fluorinated Pyrroles and Indoles

6 Conclusions

 
  • References

    • 1a Fan H, Peng J, Hamann MT, Hu J.-F. Chem. Rev. 2008; 108: 264
    • 1b Schmuck C, Rupprecht D. Synthesis 2007; 20: 3095
    • 1c Bellina F, Rossi R. Tetrahedron 2006; 62: 7213
    • 1d Jolicoeur B, Chapman EE, Thompson A, Lubell WD. Tetrahedron 2006; 62: 11531
    • 2a Hiyama T. Organofluorine Compounds. Chemistry and Applications. Springer; Berlin: 2000
    • 2b Chambers RD. Fluorine in Organic Chemistry . Blackwell; Oxford: 2004
    • 2c Kirsch P. Modern Fluoroorganic Chemistry: Synthesis, Reactivity, Applications. Wiley-VCH; Weinheim: 2004
    • 2d Uneyama K. Organofluorine Chemistry . Blackwell; Oxford: 2006
    • 2e Theodoridis G. Fluorine-containing agrochemicals: An overview of recent developments . In Advances in Fluorine Science. Vol. 2. Tressaud A. Elsevier; Amsterdam: 2006: 121-175
    • 2f Bégué JP, Bonnet-Delpon D. Bioorganic and Medicinal Chemistry of Fluorine . John Wiley & Sons; Hoboken: 2008
    • 2g Fluorine and Health. Molecular Imaging Biomedical Materials and Pharmaceuticals. Tressaud A, Haufe G. Elsevier; Amsterdam: 2008: 553-778
    • 2h Fluorinated Heterocycles . Gakh A, Kirk KL. Oxford University Press; Oxford: 2008
    • 2i Fluorinated Heterocyclic Compounds: Synthesis, Chemistry, and Applications. Petrov VA. John Wiley & Sons; Hoboken: 2009
  • 3 Purser S, Moore PR, Swallow S, Gouverneur V. Chem. Soc. Rev. 2008; 37: 320
    • 4a Lu R.-J, Tucker JA, Zinevitch T, Kirichenko O, Konoplev V, Kuznetsova S, Sviridov S, Pickens J, Tandel S, Brahmachary E, Yang Y, Wang J, Freel S, Fisher S, Sullivan A, Zhou J, Stanfield-Oakley S, Greenberg M, Bolognesi D, Bray B, Koszalka B, Jeffs P, Khasanov A, Ma Y.-A, Jeffries C, Liu C, Proskurina T, Zhu T, Chucholowski A, Li R, Sexton C. J. Med. Chem. 2007; 50: 6535
    • 4b Meanwell NA, Wallace OB, Fang H, Wang H, Deshpande M, Wang T, Yin Z, Zhang Z, Pearce BC, James J, Yeung K.-S, Qiu Z, Wright JJ. K, Yang Z, Zadjura L, Tweedie DL, Yeola S, Zhao F, Ranadive S, Robinson BA, Gong Y.-F, Wang H.-GH, Blair WS, Shi P.-Y, Colonno RJ, Lin P.-F. Bioorg. Med. Chem. Lett. 2009; 19: 1977
  • 5 Frost JM, Dart MJ, Tietje KR, Garrison TR, Grayson GK, Daza AV, El-Kouhen OF, Miller LN, Li L, Yao BB, Hsieh GC, Pai M, Zhu CZ, Chandran P, Meyer MD. J. Med. Chem. 2008; 51: 1904
  • 6 Nazare D, Will W, Matter H, Schreuder H, Ritter K, Urmann M, Essrich M, Bauer A, Wagner M, Czech J, Lorenz M, Laux V, Wehner V. J. Med. Chem. 2005; 48: 4511
  • 7 Wilkerson WW, Galbraith W, Gans-Brangs K, Grubb M, Hewes WE, Jaffee B, Kenney JP, Kerr J, Wong N. J. Med. Chem. 1994; 37: 988
  • 8 Tucci FC, Zhu Y.-F, Guo Z, Gross TD, Connors PJ, Struthers RS, Reinhart GJ, Wang X, Saunders J, Chen C. Bioorg. Med. Chem. Lett. 2002; 12: 3491
  • 9 Ruebsam F, Webber SE, Tran MT, Tran CV, Murphy DE, Zhao J, Dragovich PS, Kim SH, Li L.-S, Zhou Y, Han Q, Kissinger CR, Showalter RE, Lardy M, Shah AM, Tsan M, Patel R, LeBrun LA, Kamran R, Sergeeva MV, Bartkowski DM, Nolan TG, Norris DA, Kirkovsky L. Bioorg. Med. Chem. Lett. 2008; 18: 3616
  • 10 Bovy PR, Reitz DB, Collins JT, Chamberlain TS, Olins GM, Corpus VM, McMahon EG, Palomo MA, Koepke JP, Smits GJ, McGraw DE, Gaw JF. J. Med. Chem. 1993; 36: 101
  • 11 Eldrup AB, Prhavc M, Brooks J, Bhat B, Prakash TP, Song Q, Bera S, Bhat N, Dande P, Cook PD, Bennett CF, Carroll SS, Ball RG, Bosserman M, Burlein C, Colwell LF, Fay JF, Flores OA, Getty K, LaFemina RL, Leone J, MacCoss M, McMasters DR, Tomassini JE, Von Langen D, Wolanski B, Olsen DB. J. Med. Chem. 2004; 47: 5284
  • 12 Norman MH, Chen N, Chen Z, Fotsch C, Hale C, Han N, Hurt R, Jenkins T, Kincaid J, Liu L, Lu Y, Moreno O, Santora VJ, Sonnenberg JD, Karbon W. J. Med. Chem. 2000; 43: 4288
    • 13a Nenajdenko VG, Sanin AV, Balenkova ES. Molecules 1997; 2: 186
    • 13b Nenajdenko VG, Sanin AV, Balenkova ES. Russ. Chem. Rev. 1999; 483
    • 13c Druzhinin SV, Balenkova ES, Nenajdenko VG. Tetrahedron 2007; 63: 7753
    • 13d Nenajdenko VG, Balenkova ES. ARKIVOC 2011; (i): 246
  • 14 Muzalevskiy VM, Shastin AV, Balenkova ES, Haufe G, Nenajdenko VG. Synthesis 2010; 3905
  • 15 Serdyuk O, Butin A, Abaev V. J. Fluorine Chem. 2010; 131: 296
  • 16 Serdyuk OV, Abaev VT, Butin AV, Nenajdenko VG. Synthesis 2011; 2505
  • 17 Crestoni ME, Fornarini S. Gazz. Chim. Ital. 1989; 119: 203
  • 18 Wang J, Scott AI. Tetrahedron Lett. 1994; 35: 3679
  • 19 Wang J, Scott AI. Tetrahedron 1994; 50: 6181
  • 20 Chang MN, Biftu T, Boulton DA, Finke PE, Hammond ML, Pessolano AA, Zambias RA, Bailey P, Goldenberg M, Rackham A. Eur. J. Med. Chem. 1986; 21: 363
  • 21 Gozzo FC, Ifa DR, Eberlin MN. J. Org. Chem. 2000; 65: 3920
  • 22 Zhang Y, Shibatomi K, Yamamoto H. Synlett 2005; 2837
  • 23 Ohta T, Fukuda T, Ishibashi F, Iwao M. J. Org. Chem. 2009; 74: 8143
    • 24a Tajima T, Ishii H, Fuchigami T. Electrochem. Commun. 2001; 3: 467
    • 24b Tajima T, Ishii H, Fuchigami T. Tetrahedron Lett. 2001; 42: 4857
    • 24c Tajima T, Fuchigami T. Synthesis 2002; 2597
    • 24d Tajima T, Nakajima A, Fuchigami T. J. Org. Chem. 2006; 71: 1436
    • 25a Dvornikova E, Bechcicka M, Kamieńska-Trela K, Krówczyński A. J. Fluorine Chem. 2003; 124: 159
    • 25b Samori C, Guerrini A, Varchi G, Fontana G, Bombardelli E, Tinelli S, Beretta GL, Basili S, Moro S, Zunino F, Battaglia A. J. Med. Chem. 2009; 52: 1029
    • 26a Barnes KD, Hu Y, Hunt DA. Synth. Commun. 1994; 24: 1749
    • 26b Leroy J, Porhiel E, Bondon A. Tetrahedron 2002; 58: 6713
  • 28 Wang J, Scott AI. J. Chem. Soc., Chem. Commun. 1995; 2399
    • 29a Onda H, Toi H, Aoyama Y, Ogoshi H. Tetrahedron Lett. 1985; 26: 4221
    • 29b Toi H, Homma M, Onda H, Aoyagi K, Aoyama Y, Ogoshi H. Heterocycles 1985; 182
    • 30a Martín-Santamaría S, Carroll MA, Carroll CM, Carter CD, Pike VW, Rzepa HS, Widdowson DA. Chem. Commun. 2000; 649
    • 30b Ermolenko MS, Budylin VA, Kost AN. Chem. Heterocycl. Compd. (Engl. Transl.) 1978; 14: 752
  • 31 Wallace MB, Adams ME, Kanouni T, Mol CD, Dougan DR, Feher VA, O’Connell SM, Shi L, Halkowycz P, Dong Q. Bioorg. Med. Chem. Lett. 2010; 20: 4156
    • 32a Leroy J, Wakselman C. Can. J. Chem. 1976; 54: 218
    • 32b Leroy J, Rubinstein M, Wakselman C. J. Fluorine Chem. 1984; 25: 255
    • 32c Leroy J, Wakselman C. Tetrahedron Lett. 1994; 35: 8605
    • 32d Woller EK, Smirnov VV, DiMagno SG. J. Org. Chem. 1998; 63: 5706
  • 33 Kagabu S, Tsuji H, Kawai I, Ozeki H. Bull. Chem. Soc. Jpn. 1995; 68: 341
  • 34 Buhr G. Chem. Ber. 1973; 106: 3544
    • 35a Novikov MS, Khlebnikov AF, Sidorina ES, Kostikov RR. J. Chem. Soc., Perkin Trans. 1 2000; 231
    • 35b Khlebnikov AF, Novikov MS, Dolgikh SA, Magull J. ARKIVOC 2008; (ix): 94
    • 35c Novikov MS, Khlebnikov AF, Sidorina ES, Kostikov RR. J. Fluorine Chem. 1998; 90: 117
    • 36a Novikov MS, Khlebnikov AF, Voznyi IV, Besedina OV, Kostikov RR. Russ. J. Org. Chem. 2005; 41: 361
    • 36b Novikov MS, Khlebnikov AF, Voznyi IV, Besedina OV, Kostikov RR. Tetrahedron Lett. 2001; 42: 533
    • 36c Voznyi IV, Novikov MS, Khlebnikov AF, Kopf J, Kostikov RR. Russ. J. Org. Chem. 2004; 40: 199
  • 37 Wu K, Chen QY. Synthesis 2003; 29
  • 38 Ischikawa J, Wada Y, Fujiwara M, Sakoda K. Synthesis 2002; 1917
  • 39 Qiu ZM, Burton DJ. Tetrahedron Lett. 1994; 35: 4919
    • 40a Qiu ZM, Burton DJ. Tetrahedron Lett. 1994; 35: 1813
    • 40b Qiu ZM, Burton DJ. J. Org. Chem. 1995; 60: 6798
  • 41 Kim SK, Jun C, Kwak K, Park K, Chai K. Bull. Korean Chem. Soc. 2007; 28: 2324
    • 42a Qiu ZM, Burton DJ. Tetrahedron Lett. 1995; 36: 5119
    • 42b Kim BM, San Q.-Z, Bhatt LR, Kim SK, Chai K.-Y. Bull. Korean Chem. Soc. 2010; 31: 31
  • 43 Shi G.-Q, Cai W.-L. J. Org. Chem. 1995; 60: 6289
  • 44 Shi G.-Q, Schlosser M. Tetrahedron 1993; 49: 1445
    • 45a Takaya H, Kojima S, Murahashi S. Org. Lett. 2001; 3: 421
    • 45b Gulevich AV, Zhdanko AG, Orru RV. A, Nenajdenko VG. Chem. Rev. 2010; 110: 5235
  • 46 Uno H, Sakamoto K, Tominaga T, Ono N. Bull. Chem. Soc. Jpn. 1994; 67: 1441
  • 47 Wang Y, Zhu S. Org. Lett. 2003; 5: 745
  • 48 Surmont R, Verniest G, De Kimpe N. Org. Lett. 2009; 11: 2920
  • 49 Surmont R, Verniest G, Colpaert F, Macdonald G, Thuring JW, Deroose F, De Kimpe N. J. Org. Chem. 2009; 74: 1377
  • 50 Demange L, Ménez A, Dugave C. Tetrahedron Lett. 1998; 39: 1169
  • 51 Coe PL, Holton AG, Sleigh JH, Smith P, Tatlow JC. J. Fluorine Chem. 1983; 22: 287
  • 52 Barton DH. R, Hesse RH, Jackman JP, Pechet MM. J. Chem. Soc., Perkin Trans. 1 1977; 2604
    • 53a Hodson H, Madge DJ, Slawin AN. Z, Widdowson DA, Williams DJ. Tetrahedron 1994; 50: 1899
    • 53b Lin R, Ding S, Shi Z, Jiao N. Org. Lett. 2011; 13: 4498
    • 53c Hodson H, Madge DJ, Widdowson DA, Williams DJ. Synlett 1992; 831
    • 54a Yoshikawa K, Yokomizo A, Naito H, Haginoya N, Yoshino T, Osanai K, Ohta T, Kobayashi S, Nagata T, Mochizuki A, Watanabe K, Kanno H. Bioorg. Med. Chem. 2009; 17: 8206
    • 54b Umemoto T, Fukami S, Tomizawa G, Harasawa K, Kawada K, Tomita K. J. Am. Chem. Soc. 1990; 112: 8563
  • 55 Tius MA, Kawakami JK. Tetrahedron 1995; 51: 3997
  • 56 Eissenstat MA, Bell MR, D’Ambra TA, Alexander EJ, Daum SJ, Ackerman JH, Gruett MD, Kumar V, Estep KG. J. Med. Chem. 1995; 38: 3094
  • 57 Yin B, Wang L, Inagi S, Fuchigami T. Tetrahedron 2010; 66: 6820
  • 58 Torres JC, Garden SJ, Pinto AC, da Silva FS. Q, Boechat N. Tetrahedron 1999; 55: 1881
  • 59 Guo X, Li Y, Tao L, Wang Q, Dong L, Yu X, An H, Chang J, Wang S, Hu W, Yang Q, Cui Y, Ge Z, Song C, Pan Z. Bioorg. Med. Chem. Lett. 2011; 22: 6770
    • 60a Wang X, Seth PP, Ranken R, Swayze EE, Migawa MT. Nucleosides, Nucleotides Nucleic Acids 2004; 23: 161
    • 60b Seela F, Xu K, Chittepu P. Synthesis 2006; 2005
    • 60c Suydam IT, Strobel SA. J. Am. Chem. Soc. 2008; 130: 13639
    • 60d Seela F, Xu K. Helv. Chim. Acta 2008; 91: 1083
    • 60e Chen Y.-L, Yin Z, Duraiswamy J, Schul W, Lim CC, Liu B, Xu HY, Qing M, Yip A, Wang G, Chan WL, Tan HP, Lo M, Liung S, Kondreddi RR, Rao R, Keller TH, Shi P.-Y, Gu H, He H. Antimicrob. Agents Chemother. 2010; 54: 2932
    • 60f Hu W, Wang P, Song C, Pan Z, Wang Q, Guo X, Yu X, Shen Z, Wang S, Chang J. Bioorg. Med. Chem. Lett. 2010; 20: 7297
    • 60g Kung P.-P, Richardson P, Hickey MJ, Gajiwala KS, Wang F, Huang B, McClellan G, Wang J, Maegley K, Bergqvist S, Mehta PP, Kania R, Sinnema P.-J. Bioorg. Med. Chem. Lett. 2011; 21: 3557
  • 61 Seela F, Ming X. Tetrahedron 2007; 63: 9850
  • 62 Seela F, Xu K, Chittepu P, Ming X. Nucleosides, Nucleotides Nucleic Acids 2007; 26: 607
  • 63 Shi J, McBrayer TR, Whitaker T, Coats SJ, Zhou L, Zhang H, Detorio MA, Johns M, Bassit L, Schinazi RF, Powdrill MH, Goette M. Bioorg. Med. Chem. Lett. 2011; 21: 7094
  • 64 Evans GB, Furneaux RH, Lewandowicz A, Schramm VL, Tyler PC. J. Med. Chem. 2003; 46: 3412
    • 65a Ichikawa J, Wada Y, Okauchi T, Minami T. Chem. Commun. 1997; 1537
    • 65b Ichikawa J, Nadano R, Mori T, Wada Y. Org. Synth. 2006; 83: 111
  • 66 Banks RE, Hitchen SM, Thomson J. J. Fluorine Chem. 1982; 20: 127
  • 67 Banks RE, Mohialdin SN. J. Fluorine Chem. 1986; 34: 275
  • 68 Fang X, Wu Y.-M, Deng J, Wang S.-W. Tetrahedron 2004; 60: 5487
    • 69a Petrov VP, Barkhash VA, Shchegoleva GS, Petrova TD, Savchenko TL, Yakobson GG. Dokl. Akad. Nauk SSSR 1968; 178: 864
    • 69b Petrov VP, Barkhash VA. Chem. Heterocycl. Compd. (Engl. Transl.) 1973; 9: 573
    • 69c Petrov VP, Barkhash VA. Chem. Heterocycl. Compd. (Engl. Transl.) 1970; 6: 353
    • 70a Brooke GM. Tetrahedron Lett. 1968; 4049
    • 70b Brooke GM, Musgrave WK. R, Rutherpord RJ. D, Smith TW. Tetrahedron 1971; 27: 5653
    • 71a Fujita M, Ojima I. Tetrahedron Lett. 1983; 24: 4573
    • 71b Ojima I, Kato K, Nakahashi K. J. Org. Chem. 1989; 54: 4511
  • 72 Blazejewski J.-C, Wakselman C. J. Chem. Soc., Perkin Trans. 1 1980; 2845
  • 73 Brooke GM, Rutherford RJ. D. J. Chem. Soc. 1968; 1189
    • 74a Brooke GM. J. Chem. Soc., Perkin Trans. 1 1983; 821
    • 74b Benke FD, Brooke GM. J. Fluorine Chem. 1984; 26: 77
    • 75a Filler R, Woods SM, Freudenthal AF. J. Org. Chem. 1973; 38: 811
    • 75b Filler R, Chen W, Woods SM. J. Fluorine Chem. 1995; 73: 95
    • 75c Filler R, Woods SM, White WL. Can. J. Chem. 1989; 67: 1837
    • 75d Filler R, Woods SM. Org. Synth. 1977; 57: 80
  • 76 Shaffer MW, Platz MS. Tetrahedron Lett. 1989; 30: 6465
    • 77a Masaaki S, Ryuichiro T, Atsuhiro O. Chem. Commun. 2004; 2682
    • 77b Shimizu S, Shin J.-Y, Furuta H, Ismael R, Osuka A. Angew. Chem. Int. Ed. 2003; 42: 78
  • 78 Shohei S, Atsuhiro O. Chem.–Eur. J. 2006; 12: 9095
  • 79 Haketa Y, Sakamoto S, Chigusa K, Maeda H, Nakanishi T. J. Org. Chem. 2011; 76: 5177
  • 80 Anzenbacher P, Try AC, Miyaji H, Jursicova K, Lynch VM, Marquez M, Sessler J. J. Am. Chem. Soc. 2000; 122: 10268
  • 81 Maeda H, Ito Y, Kusunose Y, Nakanishi T. Chem. Commun. 2007; 1136
    • 82a Sessler JL, Anzenbacher P, Shriver JA, Jursikova K, Lynch VM, Marquez M. J. Am. Chem. Soc. 2000; 122: 10261
    • 82b Moyer BA, Sloop FV. Jr, Fowler CJ, Haverlock TJ, Kang H.-A, Delmau LH, Bau DM, Hossain MA, Bowman-James K, Shriver JA, Bill NL, Gross DE, Marquez M, Lynch VM, Sessler JL. Supramol. Chem. 2010; 22: 653
    • 83a Biffinger JC, Sun H, Nelson AP, DiMagno SG. Org. Biomol. Chem. 2003; 1: 733
    • 83b Leroy J, Bondon A, Toupet L, Rolando C. Chem.–Eur. J. 1997; 3: 1890
    • 83c Woller EK, DiMagno SG. J. Org. Chem. 1997; 62: 1588
    • 83d Leroy J, Bondon A, Toupet L. Acta Crystallogr., Sect. C 1999; 55: 464
    • 84a Steene E, Dey A, Ghosh A. J. Am. Chem. Soc. 2003; 125: 16300
    • 84b Liu H.-Y, Lai T.-S, Yeung L.-L, Chang CK. Org. Lett. 2003; 5: 617
    • 85a Suzuki A, Toi H, Aoyama Y, Ogoshi H. Heterocycles 1992; 33: 87
    • 85b Suzuki A, Tomizawa T, Hayashi T, Mizutani T, Ogoshi H. Bull. Chem. Soc. Jpn. 1996; 69: 2923
  • 86 Tanabe H, Ichikawa J. Chem. Lett. 2010; 39: 248
  • 87 Trost BM, Osipov M, Dong G. J. Am. Chem. Soc. 2010; 132: 15800
  • 88 Petrova TD, Savchenko TI, Shchegoleva LN, Ardyukova TF, Yakobson GG. Chem. Heterocycl. Compd. (Engl. Transl.) 1970; 6: 1251
  • 89 Campbell JA, Bordunov V, Broka CA, Dankwardt J, Hendricks RT, Kress JM, Walker KA. M, Wang J.-H. Tetrahedron Lett. 2004; 45: 3793