Synthesis of Fused Imidazoles and Benzothiazoles from (Hetero)Aromatic ortho-Diamines or ortho-Aminothiophenol and Aldehydes Promoted by Chlorotrimethylsilane

Sergey V. Ryabukhin; Andrey S. Plaskon; Dmitriy M. Volochnyuk; Andrey A. Tolmachev

doi:10.1055/s-2006-950289

PAPER

Synthesis of Fused Imidazoles and Benzothiazoles from (Hetero)Aromatic ortho-Diamines or ortho-Aminothiophenol and Aldehydes Promoted by Chlorotrimethylsilane

Sergey V. Ryabukhin^a,b, Andrey S. Plaskon^a,b, Dmitriy M. Volochnyuk*^a,c, Andrey A. Tolmachev^b
^a Enamine Ltd., 23 A. Matrosova st., 01103 Kiev, Ukraine
^b National Taras Shevchenko University, 62 Volodymyrska st., Kyiv-33, 01033 Kiev, Ukraine
^c Institute of Organic Chemistry, National Academy of Sciences of Ukraine, Murmanska 5, Kyiv-94, 02094 Kiev, Ukraine
Fax: +380(44)5373253; e-Mail: D.Volochnyuk@enamine.net;

Abstract

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Abstract

New convenient conditions for benzimidazole and benzothiazole syntheses are described. A set of benzimidazoles, 3H-imidazo[4,5-b]pyridines, purines, xanthines and benzothiazoles was readily prepared from (hetero)aromatic ortho-diamines or ortho-aminothiophenol and aldehydes using chlorotrimethylsilane in DMF as a promoter and water-acceptor agent, followed by oxidation with air oxygen.

Key words

benzimidazoles - benzothiazoles - aldehydes - chlorotrimethylsilane - parallel synthesis

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References

<A NAME="RP07306SS-1A">1a</A> Spasov AA. Yozhitsa IN. Bugaeva LI. Anisimiva VA. Pharm. Chem. J. 1999, 33: 232

<A NAME="RP07306SS-1B">1b</A> Preston PN. In The Chemistry of Heterocyclic Compounds, Benzimidazoles and Congeneric Tricyclic Compounds Part 2, Vol. 40: John Wiley and Sons; New York: 1980. Chap. 10.

<A NAME="RP07306SS-1C">1c</A> Preston PN. Chem. Rev. 1974, 74: 279

For recent examples, see:

<A NAME="RP07306SS-2A">2a</A> Buerli RW. McMinn D. Kaizerman JA. Hu W. Ge Y. Pack Q. Jiang V. Gross M. Garcia M. Tanaka R. Moser HE. Bioorg. Med. Chem. Lett. 2004, 14: 1253

<A NAME="RP07306SS-2B">2b</A> Ryu C.-K. Song E.-H. Shim J.-Y. You H.-J. Choi KU. Choi IH. Lee EY. Chae MJ. Bioorg. Med. Chem. Lett. 2003, 13: 17

<A NAME="RP07306SS-2C">2c</A> Hranjec M. Grdisa M. Pavelic K. Boykin DW. Karminski-Zamola G. Farmaco 2003, 58: 1319

<A NAME="RP07306SS-2D">2d</A> Tawar U. Jain AK. Dwarakanath BS. Chandra R. Singh Y. Chaudhury NK. Khaitan D. Tandon V. J. Med. Chem. 2003, 46: 3785

<A NAME="RP07306SS-2E">2e</A> Guemues F. Demirci AB. Oezden T. Eroglu H. Diril N. Pharmazie 2003, 58: 303

<A NAME="RP07306SS-2F">2f</A> Yang D. Fokas D. Li J. Yu L. Baldino CM. Synthesis 2005, 47

For recent examples, see:

<A NAME="RP07306SS-3A">3a</A> Beaulieu PL. Haché B. von Moos E. Synthesis 2003, 1683

<A NAME="RP07306SS-3B">3b</A> Jung MH. Park JM. Lee I.-YC. Ahn M. J. Heterocycl. Chem. 2003, 40: 37

<A NAME="RP07306SS-3C">3c</A> Reddy GV. Rao VVVNSR. Narsaiah B. Rao PS. Synth. Commun. 2002, 32: 2467

<A NAME="RP07306SS-3D">3d</A> Nagata K. Itoh T. Ishikawa H. Ohsawa A. Heterocycles 2003, 61: 93

<A NAME="RP07306SS-3E">3e</A> Ben-Alloum A. Bougrin S. Soufiaoui M. Tetrahedron Lett. 2003, 44: 5935

<A NAME="RP07306SS-4A">4a</A> Blettner CG. König WA. Rühter G. Stenzel W. Schotten T. Synlett 1999, 307

<A NAME="RP07306SS-4B">4b</A> Sun Q. Gatto B. Yu C. Liu A. Liu LF. LaVoie EJ. J. Med. Chem. 1995, 38: 3638

<A NAME="RP07306SS-4C">4c</A> Ben-Alloum A. Bakkas S. Soufiaoui M. Tetrahedron Lett. 1998, 39: 4481

<A NAME="RP07306SS-4D">4d</A> Satz AL. Bruice TC. Bioorg. Med. Chem. Lett. 1999, 9: 3261

<A NAME="RP07306SS-4E">4e</A> Rangarajan M. Kim JS. Sim S.-P. Liu A. Liu LR. LaVoie EJ. Bioorg. Med. Chem. 2000, 8: 2591

<A NAME="RP07306SS-4F">4f</A> Black DSC. Kumar N. Wong LCH. Synthesis 1986, 474

<A NAME="RP07306SS-5A">5a</A> Denny WA. Rewcastle GW. Baguley BC. J. Med. Chem. 1990, 33: 814

<A NAME="RP07306SS-5B">5b</A> Dang Q. Brown BS. Erion MD. Tetrahedron Lett. 2000, 41: 6559

<A NAME="RP07306SS-5C">5c</A> Singh MP. Sasmal S. Lu W. Chatterjee MN. Synthesis 2000, 1380

<A NAME="RP07306SS-5D">5d</A> Gravatt GL. Baguley BC. Wilson WR. Denny WA. J. Med. Chem. 1994, 37: 4338

<A NAME="RP07306SS-5E">5e</A> Das TM. Rao CP. Kalle N. Rissanen K. Indian J. Chem., Sect. B: Org. Chem. Incl. Med. Chem. 2003, 42: 661

<A NAME="RP07306SS-6A">6a</A> Vanden Eynde JJ. Delfosse F. Lor P. Van Haverbeke Y. Tetrahedron 1995, 51: 5813

<A NAME="RP07306SS-6B">6b</A> Hopkins KT. Wilson WD. Bender BC. McCurdy DR. Hall JE. Tidwell RR. Kumar A. Bajic M. Boykin DW. J. Med. Chem. 1998, 41: 3872

<A NAME="RP07306SS-6C">6c</A> Lombardy RL. Tanious FA. Ramachandran K. Tidwell RR. Wilson WD. J. Med. Chem. 1996, 39: 1452

<A NAME="RP07306SS-6D">6d</A> Starcevic K. Boykin DW. Karminski-Zamola G. Heterocycl. Commun. 2002, 8: 221

<A NAME="RP07306SS-7">7</A> Chikashita H. Nishida S. Miyazaki M. Morita Y. Itoh K. Bull. Chem. Soc. Jpn. 1987, 60: 737

<A NAME="RP07306SS-8">8</A> Pätzold F. Zeuner F. Heyer TH. Niclas H.-J. Synth. Commun. 1992, 22: 281

<A NAME="RP07306SS-9">9</A> Risitano F. Grassi G. Foti F. Bilardo C. Heterocycles 2001, 55: 1311

<A NAME="RP07306SS-10A">10a</A> Ridley HF. Spickett RGW. Timmis GM. J. Heterocycl. Chem. 1965, 2: 453

<A NAME="RP07306SS-10B">10b</A> Göker H. Kus C. Boykin DW. Yildiz S. Altanlar N. Bioorg. Med. Chem. 2002, 10: 2589

<A NAME="RP07306SS-10C">10c</A> Meric A. Incesu Z. Isikdag I. Farmaco 2002, 57: 543

<A NAME="RP07306SS-11">11</A> Kawashita Y. Nakamichi N. Kawabata H. Hayashi M. Org. Lett. 2003, 5: 3713

For use of Me₃SiCl as a condensation agent, see:

<A NAME="RP07306SS-12A">12a</A> Ryabukhin SV. Plaskon AS. Tverdokhlebov AV. Tolmachev AA. Synth. Commun. 2004, 34: 1483

<A NAME="RP07306SS-12B">12b</A> Ryabukhin SV. Plaskon AS. Volochnyuk DM. Tolmachev AA. Synlett 2004, 2287

<A NAME="RP07306SS-12C">12c</A> Zhu Y.-L. Huang S.-L. Pan Y.-J. Eur. J. Org. Chem. 2005, 2354

<A NAME="RP07306SS-12D">12d</A> Zhu Y.-L. Pan Y.-J. Huang S.-L. Synth. Commun. 2004, 34: 3167

<A NAME="RP07306SS-12E">12e</A> Heaney H. Papageorgeogu G. Wilkins RF. Tetrahedron 1997, 53: 2941

For use of Me₃SiI as a condensation agent, see:

<A NAME="RP07306SS-12F">12f</A> Sabitha G. Reddy GSKK. Reddy KB. Yadav JS. Synthesis 2004, 263

<A NAME="RP07306SS-12G">12g</A> Sabitha G. Reddy GSKK. Reddy CS. Yadav JS. Synlett 2003, 858

<A NAME="RP07306SS-12H">12h</A> Sabitha G. Reddy GSKK. Reddy CS. Yadav JS. Tetrahedron Lett. 2003, 44: 4129

For recent examples of the synthesis of benzothiazoles starting from o-aminothiophenol and aldehydes, see:

<A NAME="RP07306SS-13A">13a</A> Itoh T. Nagata K. Ishikawa H. Ohsawa A. Heterocycles 2004, 62: 197

<A NAME="RP07306SS-13B">13b</A> Ben-Alloum A. Bakkas S. Soufiaoui M. Tetrahedron Lett. 1997, 38: 6395

<A NAME="RP07306SS-14">14</A> For recent examples of the synthesis of benzoxazoles starting from o-aminophenoles and aldehydes, see ref. 11 and: Chang J. Zhao K. Pan S. Tetrahedron Lett. 2002, 43: 951

For recent examples of the synthesis of 3H-imidazo[4,5-b]pyridines from 2,3-diaminopyridines and aldehydes, see ref. 5c and:

<A NAME="RP07306SS-15A">15a</A> Singh AK. Lown JW. Synth. Commun. 2000, 30: 923

<A NAME="RP07306SS-15B">15b</A> Oguchi M. Wada K. Honma H. Tanaka A. Kaneko T. Sakakibara S. Ohsumi J. Serizawa N. Fujiwara T. Horikoshi H. Fujita T. J. Med. Chem. 2000, 43: 3052

<A NAME="RP07306SS-15C">15c</A> Blettner CG. Koenig WA. Ruehter G. Stenzel W. Schotten T. Synlett 1999, 307

<A NAME="RP07306SS-16">16</A> For examples of the synthesis of 2,6-diaminopurines starting from 2,4,5,6-tetraaminopyrimidine and aldehydes, see: Gangjee A. Vasudevan A. Queener SF. J. Med. Chem. 1997, 40: 3032

For recent examples of synthesis of xanthines from 5,6-diaminouracils and aldehydes, see:

<A NAME="RP07306SS-17A">17a</A> De Araujo AD. Bacher E. Demnitz FWJ. Santos DA. Heterocycles 1999, 51: 29

<A NAME="RP07306SS-17B">17b</A> Mueller CE. Shi D. Manning M. Daly JW. J. Med. Chem. 1993, 36: 3341

<A NAME="RP07306SS-17C">17c</A> Kuefner-Muehl U, Weber KH, Walther G, Stransky W, Ensinger H, Schingnitz G, Kuhn FJ, and Lehr E. inventors; DE 03843117. ; Chem. Abstr. 1991, 114, 164265p

<A NAME="RP07306SS-18">18</A> For the synthesis of purines from 6-(substituted)amino-5-aminopyrimidines and aldehydes using FeCl₃/SiO₂, see: Liu J. Dang Q. Wei Z. Bai X. J. Comb. Chem. 2005, 7: 627

<A NAME="RP07306SS-19A">19a</A> Jahn U. Schroth W. Tetrahedron Lett. 1993, 34: 5863

<A NAME="RP07306SS-19B">19b</A> Schroth W. Jahn U. Stroehl D. Chem. Ber. 1994, 127: 2013

<A NAME="RP07306SS-20A">20a</A> Kalle A.-G. inventors; DE 1137625. 1958, Chem. Abstr. 1963, 59, 11515c

<A NAME="RP07306SS-20B">20b</A> Bunnett JF. Hrutfiord BF. J. Am. Chem. Soc. 1961, 83: 1691

<A NAME="RP07306SS-20C">20c</A> Nagase R. Kawashima T. Yoshifuji M. Heterocycles 1977, 8: 243

<A NAME="RP07306SS-20D">20d</A> Cerniani A. Passerini R. J. Chem. Soc. 1954, 2261

<A NAME="RP07306SS-20E">20e</A> Anthony K., Brown R. G., Hepworth J. D., Hodson K. W., May B., West M. A.; J. Chem. Soc., Perkin Trans. 2; 1984, 2111

<A NAME="RP07306SS-20F">20f</A> CohenV VI. J. Heterocycl. Chem. 1979, 16: 13

<A NAME="RP07306SS-20G">20g</A> Szczepankiewicz BG. Rohde JJ. Kurukulasuriya R. Org. Lett. 2005, 7: 1833

<A NAME="RP07306SS-20H">20h</A> Dubey PK. Kumar R. Vino D. Indian J. Chem., Sect. B: Org. Chem. Incl. Med. Chem. 2000, 39: 746

<A NAME="RP07306SS-21A">21a</A> Young RC. Jones M. Milliner KJ. Rana KK. Ward JG. J. Med. Chem. 1990, 33: 2073

<A NAME="RP07306SS-21B">21b</A> Mueller CE. Thorand M. Qurishi R. Diekmann M. Jacobson KA. Padgett WL. Daly JW. J. Med. Chem. 2002, 45: 3440

<A NAME="RP07306SS-22">22</A> Nicolai E. Goyard J. Benchetrit T. Teulon JM. Caussade F. Virone A. Delchambre C. Cloarec A. J. Med. Chem. 1993, 36: 1175

<A NAME="RP07306SS-23">23</A> Sato K, Kitaguchi H, Takechi M, Tsukase M, and Kato M. inventors; JP 182039. ; Chem. Abstr. 1987, 106, 147020x

<A NAME="RP07306SS-24">24</A> Curran WV. Angier RB. J. Am. Chem. Soc. 1958, 80: 6095

<A NAME="RP07306SS-25">25</A> McClure MS. Roschangar F. Hodson SJ. Millar A. Osterhout MH. Synthesis 2001, 1681

<A NAME="RP07306SS-26">26</A> Bebernitz GR. Argentieri G. Battle B. Brennan C. Balkan B. Burkey BF. Eckhardt M. Gao J. Kapa P. Stroehschein RJ. Schuster HF. Wilson M. Xu DD. J. Med. Chem. 2001, 44: 2601

<A NAME="RP07306SS-27">27</A> Kristek F. Klicnar J. Vetersnik P. Collect. Czech. Chem. Commun. 1971, 36: 3608