Russian Federation
Russian Federation
New reactions, which have been discovered and continue to be developed in A.E. Favorsky Irkutsk institute of chemistry SB RAS on the basis of acetylene, a product of oil, gas and coal processing and multi-faceted building block for organic synthesis, have been considered. These reactions provide for the shortest routes to construction of fundamental heterocyclic scaffolds (pyrroles, imidazoles, pyrazoles, indoles, pyridines, dihydropyridines, etc.) with desirable and optimum combination of functional pharmacophoric groups and fragments, which are responsible for antiviral (HIV, flu), antitumor, tuberculostatic and hypotensive activities.
acetylene and its derivatives, nitrogen-containing heterocycles, nucleophiles, zwitter-ions, atom-economic addition reactions, drug precursors
Создание новых методологий направленного синтеза высокоэффективных средств профилактики и лечения социально значимых заболеваний (сердечно-сосудистые и онкологические заболевания, туберкулёз, грипп, теросклероз, ВИЧ/СПИД-инфекция) относится к прорывным научным исследованиям, имеющим высокую степень реализации на мировом уровне. В Иркутском институте химии им. А.Е. Фаворского СО РАН (ИрИХ) эта фундаментальная задача решается в первую очередь на основе новых реакций ацетилена и его производных [1–6].
1. Trofimov B.A., Gusarova N.K. Acetilen: novye vozmozhnosti klassicheskih reakciy // Uspehi himii. - 2007. - T. 76, № 6. - S. 550.
2. Trofimov B.A., Mihaleva A.I., Shmidt E.Yu., Sobenina L.N. Himiya pirrola. Novye stranicy / Pod red. G.A. Tolstikova. - Novosibirsk: Nauka, 2012. - 383 s. - ISBN 978-5-02-019070-2.
3. Gusarova N.K., Mihaleva A.I., Shmidt E.Yu., Mal'kina A.G. Himiya acetilena. Novye glavy / Pod red. M.P. Egorova. - Novosibirsk: Nauka, 2013. - 368 s. - ISBN 978-5-02-019116-7.
4. Trofimov B.A., Mikhaleva A.I., Schmidt E.Yu., Sobenina L.N. Chemistry of pyrroles // CRC Press Taylor & Fransis Group. - 2014. - 398 p. - ISBN 13:978-1-4822-3242-4.
5. Trofimov B.A., Shmidt E.Yu. Reakcii acetilenov v superosnovnyh sredah - itogi poslednih let // Uspehi himii. - 2014. - T. 83, № 7. - S. 600.
6. Sobenina L.N., Tomilin D.N., Trofimov B.A. C-etinilpirroly: sintez i reakcionnaya sposobnost' // Uspehi himii. - 2014. - T. 83, № 6 - S. 475.
7. Trofimov B.A., Schmidt E.Yu., Ushakov I.A., Zorina N.V. et al. Base-catalyzed stereoselective vinylation of ketones with arylacetylenes: a new C(SP3)-C(SP2) bond-forming reaction // Chem. Eur. J. - 2010. - Vol. 16, N 28 - P. 8516.
8. Trofimov B.A., Schmidt E.Yu., Zorina N.V., Ivanova E.V. et al. Transition metal-free stereoselective α-vinylation of cyclic ketones with arylacetylenes in the superbasic catalytic triad potassium hydroxide/tert-butyl alcohol/dimethyl sulfoxide // Adv. Synth. Catal. - 2012. - Vol. 354, N 9. - P. 1813.
9. Trofimov B.A., Schmidt E.Yu., Zorina N.V., Ivanova E.V. et al. Transition-metal-free superbasepromoted stereoselective α-vinylation of ketones with arylacetylenes: a general strategy for synthesis of β, γ-unsaturated ketones // J. Org. Chem. - 2012. - Vol. 77. - P. 6880.
10. Schmidt E.Yu., Bidusenko I.A., Cherimichkina N.A., Ushakov I.A. et al. Furans conjugated with bulky aromatic systems: one-pot synthesis from ketones and acetylene // Chem. Eur. J. - 2015. - Vol. 21, N 45. - P. 15944.
11. Schmidt E.Yu., Ivanova E.V., Tatarinova I.V., Ushakov I.A. et al. Synthesis of acyl terphenyls and higher polyaromatics via base-promoted C-H functionalization of acetylarenes with arylacetylenes // Org. Lett. - 2016. - Vol. 18, N 9. - P. 2158.
12. Trofimov B.A., Schmidt E.Yu., Ushakov I.A., Mikhaleva A.I. et al. One-pot assembly of 7-methylene-6,8-dioxabicyclo[3.2.1]octanes, congeners of frontalin, from ketones and acetylene // Eur. J. Org. Chem. - 2009. - N 30. - P. 5142-5145.
13. D’Cruz O.J., Waurzyniak B., Uckun F.M. Antiretroviral spermicide WHI-07 prevents vaginal and rectal transmission of feline immunodeficiency virus in domestic cats // Antimicrob. Agents Chemother. - 2004. - Vol. 48, N 4. - P. 1082-1088.
14. Hartiger C.G., Dyson P. Bioorganometallic chemistry--from teaching paradigms to medicinal applications // Chem. Soc. Rev. - 2009. - Vol. 38, N 2. - P. 391-401.
15. Li Z., Nakashige M., Chain W.J. A brief synthesis of (-)-englerin A // J. Am. Chem. Soc. - 2011. - Vol. 133, N 17. - P. 6553-6556.
16. Wood J.L., Pujanauski B.G., Sarpong R. Synthesis of the tetracyclic core of the neomangicols using a latestage indene alkylation // Org. Lett. - 2009. - Vol. 11, N 14. - P. 3128-3131.
17. Banerjee S., Ghosh S., Sinha S., Ghosh S.J. Convenient route to both enantiomers of a highly functionalized trans-disubstituted cyclopentene. Synthesis of the carbocyclic core of the nucleoside BCA // Org. Chem. - 2005. Vol. 70, N 10. - P. 4199-4202.
18. De Luca L., Ferro S., Gitto R., Barreca M.L. et al. Small molecules targeting the interaction between HIV-1 integrase and LEDGF/p75 cofactor // Bioorg. Med. Chem. - 2010. - Vol. 18, N 21. - P. 7515-7521.
19. Hu G., Li X., Zhang X., Li Y. et al. Discovery of inhibitors to block interactions of HIV-1 integrase with human LEDGF/p75 via structure-based virtual screening and bioassays // J. Med. Chem. - 2012. - Vol. 55, N 22. - P. 10108-10117.
20. Trofimov B.A., Mihaleva A.I. N-vinilpirroly. - Novosibirsk: Nauka. 1984. - 264 s.
21. Bellorini M., Moncollin V., D’Incalci M., Mongelli N. Distamycin A and tallimustine inhibit TBP binding and basal in vitro transcription // Nucleic Acids Res. - 1995. - Vol. 23, N 10. - P. 1657-1663.
22. Sharma L., Sattigeri J.A., Kumar N., Yadav A. et al. Pyrrole carboxylic acid derivatives as antibacterial agents: Patent EP 2326640. - 2009.
23. Liu Y., Zhong W., Li R.J., Li S. Synthesis of potent inhibitors of β-ketoacyl-acyl carrier protein synthase III as potential antimicrobial agents // Molecules. - 2012. - Vol. 17, N 5. - P. 4770-4781.
24. Lee J.Y., Yoon K.J., Lee Y.S. Catechol-substituted L-chicoric acid analogues as HIV integrase inhibitors // Bioorg. Med. Chem. Lett. - 2003. - Vol. 13, N 24. - P. 4331-4334.
25. Zhang P., Chen X., Li D., Fang Z. et al. HIV-1 NNRTIs: structural diversity, pharmacophore similarity, and implications for drug design // Med. Res. Rev. - 2013. - Vol. 33, Suppl. 1. - P. E1-E72.
26. Shabalin D.A., Dvorko M.Yu., Schmidt E.Yu., Protsuk N.I. et al. Reaction of (het)aryl cyclohexyl ketoximes with acetylene in the two-phase KOH/DMSO/n-hexane system: en route to spirocyclic 3H-pyrroles // Mendeleev Commun. - 2015. - Vol. 25, N 2. - P. 129.
27. Trofimov B.A., Stepanov A.V., Mal’kina A.G., Volostnykh O.G. Expedient access to functionalized Furan/3(2H)-Furanone ensembles via microwave assisted domino reactions // Synthetic Commun. - 2015. - Vol. 45, N 23. - P. 2718-2729.
28. Trofimov B.A., Andriyankova L.V., Nikitina L.P., Belyaeva K.V. Raskrytie piridinovogo kol'ca benzoilfenilacetilenom v prisutstvii vody s obrazovaniem 5-amino-2,4-pentadienaley // Zhurnal organicheskoy himii. - 2015. - T. 51, № 7. - S. 1055.
29. Trofimov B.A., Shemyakina O.A., Mal’kina A.G., Stepanov A.V. et al. Organic superbases in annulation with propargylic alcohols: straightforward synthesis of the functionalized oxazolopyrrolohexahydropy rimidine and oxazolohexahydropyrimidoazepine scaffolds // Eur. J. Org. Chem. - 2016. - Vol. 2016, N 33. - P. 5465-5469.
30. Shabalin D.A., Dvorko M.Yu., Schmidt E.Yu., Ushakov I.A. et al. 3H-pyrroles from ketoximes and acetylene: synthesis, stability and quantum-chemical insight // Tetrahedron. - 2015. - Vol. 71, N 21. - P. 3273-3281.
31. Kleemann A., Engel J., Kutscher B., Reichert D. Pharmaceutical substances: synthesis, patents, applications. - Stuttgart, New York: Thieme, 2001. - P. 31.
32. Guillarme S., Legoupy S., Bourgougnon N., Aubertinc A.-M. et al. Synthesis of new acyclonucleosides comprising unexpected regioisomers in the case of purines // Tetrahedron. - 2003. - Vol. 59, N 48. - P. 9635-9639.
33. Meier C., Habel C., Haller-Meier F., Lomp A. et al. Chemistry and anti-herpes simplex virus type 1 evaluation of cycloSal-nucleotides of acyclic nucleoside analogues // Antiviral Chem. Chemother. - 1998. - Vol. 9, N 5. - P. 389-402.
34. Fisher E.J., Chaloner K., Cohn D.L., Grant L.B. et al. The safety and efficacy of adefovir dipivoxil in patients with advanced HIV disease: a randomized, placebo-controlled trial // AIDS. - 2001. - Vol. 15, N 13. - P. 1695-1700.
35. Kotian P.L., Satish Kumar V., Lin T.-H., El-Kattan Y. An efficient synthesis of acyclic N7- and N9-adenine nucleosides via alkylation with secondary carbon electrophiles to introduce versatile functional groups at the C-1 position of acyclic moiety // Nucleosides, Nucleotides, Nucleic Acids. - 2006. - Vol. 25, N 2. - P. 121-140.
36. Belyaeva K.V., Andriyankova L.V., Nikitina L.P., Bagryanskaya I.Yu. Reaction of 1-substituted benzimidazoles with acylacetylenes and water: ringopening versus ring-expansion and isotopic effect of deuterium // Tetrahedron. 2015. - Vol. 71, N 19. - P. 2891-2899.
37. Trofimov B.A., Andriyankova L.V., Nikitina L.P., Belyaeva K.V. et al. (Imidazol-2-yl)methyl-1,3-propanediones: regioselective C-H functionalization of the imidazole ring by acylacetylene/aldehyde pairs // Eur. J. Org. Chem. 2016. - Vol. 2016, N 6. - P. 1199-1204.
38. Trofimov B.A., Nikitina L.P., Andriyankova L.V., Belyaeva K.V. i dr. Pervyy primer nekataliticheskoy C2-H funkcionalizacii imidazol'nogo kol'ca alkoksienonovoy sistemoy // Zhurnal organicheskoy himii. - 2016. - T. 52, № 4. - S. 614-616.
39. Wilson W.D., Nguyen B., Tanious F.A., Mathis A. et al. Dications that target the DNA minor groove: compound design and preparation, DNA interactions, cellular distribution and biological activity // Curr. Med. Chem. Anticancer Agents. - 2005. - Vol. 5, N 4. - P. 389-408.
40. Refaat H.M. Synthesis and anticancer activity of some novel 2-substituted benzimidazole derivatives // Eur. J. Med. Chem. - 2010. - Vol. 45, N 7. - P. 2949-2956.
41. Estrada-Soto S., Villalobos-Molina R., Aguirre-Crespo F., Vergara-Galicia J. et al. Relaxant activity of 2-(substituted phenyl)-1H-benzimidazoles on isolated rat aortic rings: design and synthesis of 5-nitro derivatives // Life Sci. - 2006. - Vol. 79, N 5. - P. 430-435.
42. Shah D.I., Sharma M., Bansal Y., Bansal G. Angiotensin II-AT1 receptor antagonists: design, synthesis and evaluation of substituted carboxamido benzimidazole derivatives // Eur. J. Med. Chem. - 2008. - Vol. 43, N 9. - P. 1808-1812.
43. Middleton T., Lim H.B., Montgomery D., Rockway T. et al. Inhibition of human immunodeficiency virus type I integrase by naphthamidines and 2-aminobenzimidazoles // Antivir. Res. - 2004. - Vol. 64, N 1. - P. 35-45.
44. Chong P., Sebahar P., Youngman M., Garrido D. et al. Rational design of potent non-nucleoside inhibitors of HIV-1 reverse transcriptase // J. Med. Chem. - 2012. - Vol. 55, N 23. - P. 10601-10609.
45. Shingalapur R.V., Hosamani K.M., Keri R.S. Synthesis and evaluation of in vitro anti-microbial and anti-tubercular activity of 2-styryl benzimidazoles // Eur. J. Med. Chem. - 2009. - Vol. 44, N 10. - P. 4244-4248.
46. Gusarova N.K., Volkov P.A., Ivanova N.I., Arbuzova S.N. et al. One-pot reductive N-vinylation and C(4)-phosphorylation of pyridines with alkyl propiolates and secondary phosphine chalcogenides // Tetrahedron Lett. - 2015. -Vol. 56, N 33. - P. 4804-4806.
47. Gusarova N.K., Volkov P.A., Ivanova N.I., Hrapova K.O. i dr. Ctericheskiy kontrol' regionapravlennosti vosstanovitel'nogo N-vinilirovaniya-S-fosforilirovaniya piridinov sistemoy alkilpropiolat vtorichnyy fosfinoksid // Zhurnal obschey himii. - 2016. - T. 86, № 3. - S. 538-541.
48. Gusarova N.K., Volkov P.A., Ivanova N.I., Khrapova K.O. et al. One-pot regio- and stereoselective synthesis of tertiary phosphine chalcogenides with (E)-N-ethenyl-1,2-dihydroquinoline functionalities // Tetrahedron Lett. -2016. - Vol. 57, N 33. - P. 3776-3780.
49. Trofimov B.A., Nedolya N.A., Tarasova O.A., Sobenina L.N. et al. A short-cut to 2,7-dihydrothiopyrano[2,3- b ]pyrrole // J. Sulfur Chem. - 2015. - Vol. 36, N 6. - P. 630-636.
50. Nedolya N.A., Tarasova O.A., Albanov A.I., Trofimov B.A. Further developments in the reaction of 2-aza-1,3,5-trienes with superbases: competitive formation of new 4,5-dihydro-1,3-thiazoles, dihydroazepines, and azepines by tandem deprotonation-cyclization // Synthesis. - 2015. - Vol. 47, N 22. - P. 3593-3610.
51. Nedolya N.A., Tarasova O.A., Albanov A.I., Trofimov B.A. One-Pot Synthesis and Intramolecular Cyclization of 5-(Prop-2-ynylsulfanyl)-1H-pyrrol-2-amines: A Simple Approach to 2,7-Dihydrothiopyrano[2,3-b]pyrrol-6-amines // Synthesis. - 2016. - Vol. 48, N 23. - P. 4278-4294.
52. Shakya N., Garg G., Agrawal B., Kumar R. Chemotherapeutic interventions against tuberculosis // Pharmaceuticals. - 2012. - Vol. 5, N 7. - P. 690-718.
53. Biava M., Porretta G.C., Manetti F. New derivatives of BM212: A class of antimycobacterial compounds based on the pyrrole ring as a scaffold // Mini-Rev. Med. Chem. - 2007. - Vol. 7, N 1. - P. 65-78.
54. Joshi S.D., More U.A., Kulkarni V.H., Aminabhavi T.M. Pyrrole: chemical synthesis, microwave assisted synthesis, reactions and applications: a review // Curr. Org. Chem. - 2013. - Vol. 17, N 20. - P. 2279-2304.
55. Ivachtchenko A.V., Ivanenkov Y.A. Small molecule 5-HT6R ligands: a comprehensive insight into their selectivity and activity // Curr. Bioact. Compd. - 2013. - Vol. 9, N 1. - P. 64-100.
56. Smith A.B. 3rd, Cho Y.S., Pettit G.R., Hirschmann R. Design, synthesis, and evaluation of azepine-based cryptophycin mimetics // Tetrahedron. - 2003. - Vol. 59. - P. 6991-7009.
57. Antonucci T., Warmus J.S., Hodges J.C., Nickell D.G. Characterization of the antiviral activity of highly substituted pyrroles: a novel class of non-nucleoside HIV-1 reverse transcriptase inhibitor // Antiviral Chem. Chemother. -
58. - Vol. 6. - P. 98-108.
59. Parshina L.N., Trofimov B.A. Sintez, stroenie i biologicheskaya aktivnost' metallokompleksov N-alkenilimidazolov // Izvestiya AN. Seriya «Himicheskaya». - 2011. - № 4. - S. 589.
60. Proizvodnye 1-alkenilimidazolatrofimov: Pat. 2397175 Ros. Federaciya / Trofimov B.A., Samoylov N.N., Babaniyazov H.H., Stankevich V.K. i dr. - № 2008151416/14; zareg. 25.12.2008; opubl. 20.08.2010, Byul. № 23.
61. Sposob polucheniya propargilovyh efirov polisaharida arabinogalaktana: Pat. 2425843 Ros. Federaciya / Trofimov B.A., Parshina L .N., Grischenko L .A. - № 2010106125/13; zareg. 19.02.2010; opubl. 10.08.2011, Byul. № 22.
62. Proizvodnye 1-allilimidazola: Pat. 2430090 Ros. Federaciya / Trofimov B.A., Babaniyazov H.H., Stankevich V.K., Nechiporenko S.P. i dr. - № 2009139214/04; zareg. 26.10.2009; opubl. 27.09.2011, Byul. № 27.
63. Sposob polucheniya tetra(1-vinilimidazol) kobal'tdihlorida: Pat. 2473553 Ros. Federaciya / Trofimov B.A., Gusarova N.K., Shantroha A.V., Parshina L .N. i dr. - № 2011148117/04; zareg. 25.11.2011; opubl. 27.01.2013, Byul. № 3.
64. Huq F., Tayyem H., Beale P., Yu J.Q. Studies on the activity of three palladium(II) compounds of the form: trans-PdL2Cl2 where L=2-hydroxypyridine, 3-hydroxypyridine, and 4-hydroxypyridine // J. Inorg. Biochem. - 2007. - Vol. 101, N 1. - P. 30-35.
65. Santini C., Pellei M., Gandin V., Porchia M. et al. Advances in copper complexes as anticancer agents // Chem. Rev. - 2014. - Vol. 114, N 1. - R. 815-862.
66. Mihaylenko V.L., Kizhnyaev V.N., Verhoturova S.I., Aparcin K.A. Sintez i svoystva novogo semeystva fosfor-azotsoderzhaschih ionenov // Doklady AN. - 2015. - T. 465, № 4. - S. 446.
67. Mihaylenko V.L., Kizhnyaev V.N., Verhoturova S.I., Aparcin K.A. i dr. Fosforsoderzhaschie ioneny // Fundamental'nye nauchnye issledovaniya: teoreticheskie i prakticheskie aspekty: Sb. mater. II Mezhdunar. nauch.-prakt. konf. - Kemerovo, 2016. - T. 2. - S. 83. - ISBN 978-5-9908668-5-0.
