Chemistry of Stable Carbenes and «Green» Technologies

TitleChemistry of Stable Carbenes and «Green» Technologies
Publication TypeJournal Article
Year of Publication2015
AuthorsKorotkikh, NI, Saberov, VSh., Rayenko, GF, Glinyanaya, NV, Knishevitsky, АV, Shvaika, ОP
Short TitleNauka innov.
SectionThe World of Innovations

Brief analysis of fundamental research in the chemistry of stable carbenes and applications in the field of «green» chemistry on their basis carried out at the L.M. Litvinenko Institute of Physical Organic & Coal Chemistry of NAS of Ukraine over the last decade is given. Carbene versions of ester Claisen condensation to form zwitterionic compounds, the Leuckart-Wallach reaction with the autoreduction of carbenoid azolium salts, Hofmann cleavage of aminocarbene insertion products, an induced tandem autotransformation of 1,2,4-triazol-5-ylidenes into 5-amidino-1,2,4-triazoles were found. New carbene reactions of ad dition, deesterification, oxidation and complexation were revealed. Effective methods of obtaining stable carbenes and carbenoids were suggested. New types of carbenes, namely benzimidazolylidenes, superstable conjugated biscarbenes and new types of carbenoids were synthesized. The existence of hypernucleophilic carbenes was theoretically predicted and experimentally confirmed. The prospects of the use of carbenes and their derivatives, in particular, carbene complexes of transition metals in catalysis of organic reactions and the search of biologically active compounds were shown.

Keywordsbiological activity, catalysis, heteroaromatic carbenes, properties, synthesis, transformations, «green» chemistry
1. Shvajka O.P., Korotkih N.I., Aslanov A.F. Geteroaromaticheskie karbeny. Himija geterocikl. soed. 1992, N 9: 1155-1170 [in Russian].
2. Igau A., Grutzmacher H., Baceiredo A., Bertrand G. Analogous a,a′-Bis-Carbenoid Triply Bonded Species: Synthesis of a Stable l3-Phosphinocarbene-l5-Phosphaacetylene. J. Amer. Chem. Soc. 1988. V. 110: 6463-6466.
3. Igau A., Baceiredo A., Trinquier G., Bertrand G. Bis(diisopropylamino)phosphino trimethylsilylcarbene: A Stable Nucleophilic Carbene. Angew. Chem. Int. Ed. Engl. 1989, V. 28: 621-622.
4. Gillette G.R., Baceiredo A., Bertrand G. Spontaneous Formation of StabIe Phosphino(silyl)- carbenes from Unstable Diazo Compounds. Angew. Chem. Int. Ed. 1990, V. 102: 1429-1431.
5. Arduengo A.J., Harlow R.L., Kline M. A stable crystalline carbine. J. Amer. Chem. Soc. 1991, V. 113: 361-362.
6. (a) Korotkih M.I., Shvajka O.P. Karbenovyj ta karbenokompleksnyj kataliz organichnyh reakcij. Donec'k: DonNU, 2013. (b) Korotkikh N. I., Shvaika O. P. Organic reactions catalysis by carbenes and metal carbene complexes, LAP Lambert Academic Publishing, 2015 [in Ukrainian].
7. Arduengo A.J., Dias H.V.R., Harlow R.L., Kline M. Electronic stabilization of nucleophilic carbenes. J. Amer. Chem. Soc. 1992, 114: 5530-534.
8. Enders D., Breuer K., Raabe G. et al. Preparation, Structure, and Reactivity of 1,3,4-Triphenyl-4,5-dihydro-lH-l,2,4-triazol-5-ylidene, a New Stable Carbene. Angew. Chem., Int. Ed. Engl. 1995, 34(9): 1021-1023.
9. Enders D., Breuer K., Runsink J., Teles J. H. Chemical Reactions of the Stable Carbene 1,3,4-Triphenyl-4,5-dihydro-1H-1,2,4-triazol-5-ylidene. Liebigs Ann. Chem. 1996: 2019-2028.
10. Korotkyh M. I., Raenko G. F., Pehtereva T. M., Shvajka O. P. Vklynennja geteroaromatychnyh karbeniv v S-N zv’jazok acetonytrylu. Dop NAN Ukrai'ny. 1998, N 6: 149-152 [in Ukrainian].
11. Korotkikh N.I., Rayenko G.F. , Shvaika O.P. Heteroaromatic carbenes of benzimidazole and 1,2,4-triazole series and their transformations with electrophilic agents. Report at the 17-th Congress of Heterocyclic Chemistry, (Vienna, 1999). Vienna, 1999. PO-383.
12. Raenko G.F., Korotkih N.I., Pehtereva T.M., Shvajka O.P. Adamantilirovanie imidazolov i benzimidazola. Zhurn. org. him. 2001, 37(8): 1212-1216 [in Russian].
13. Korotkyh N.Y., Rajenko G.F., Shvajka O.P. Novi pidhody do syntezu stabil'nyh geteroaromatychnyh karbeniv. Dop. NAN Ukrai'ny. 2000, N 2: 135-140 [in Ukrainian].
14. Korotkikh N.I., Raenko G.F., Pekhtereva T.M. et al. Stable Carbenes. Synthesis and Properties of Benzimidazol-2-ylidenes. Rus. J. Org. Chem. 2006, 42(12): 1822-1833.
15. Korotkikh N.I., Rayenko G. F., Shvaika O. P. et al. Synthesis of 1,2,4-Triazol-5-ylidenes and Their Interaction with Acetonitrile and Chalcogens. J. Org. Chem. 2003, 68(14): 5762-5765.
16. Korotkih M.I., Kysel'ov A.V., Rajenko G.F. ta in. Pershyj stabil'nyj kon’jugovanyj biskarben. Dop. NAN Ukrai'ny. 2003, N 6: 142-146 [in Ukrainian].
17. Kiselyov A.V., Korotkikh N.I., Cowley A.H. et. al. Synthesis of heteroaromatic conjugated biscarbenes of the 1,2,4-triazole series and their properties. ARKIVOC. 2008, N 15: 329-342.
18. Knishevitsky A.V., Korotkikh N.I., Cowley A.H. et. al. Copper(I) Halide Complexes of the New 4,4’-Bridged Heteroaromatic Biscarbenes of the 1,2,4-Triazole Series. J. Organomet. Chem. 2008, V. 693: 1405-1411.
19. Knishevitsky A.V., Korotkikh N.I., Cowley A.H. et. al. A Base Induced Transformation of a 1,3-Dimethyl-1,3-di(1-adamantyl)form-amidinium Salt into β-[Methyl-(1-adamantyl)amino]acrylonitriles in Aliphatic Nitriles. ARKIVOC. 2012, N 2: 60-73.
20. Korotkih M.I., Kysel'ov A.V., Pehtereva T.M. ta in. Helatni geteroaromatychni anionokarbenovi kompleksy — novyj typ karbenoi'dnyh struktur. Dop. NAN Ukrai'ny. 2005, N 6: 150–155 [in Ukrainian].
21. Korotkikh N.I., Shvaika O.P., Rayenko G.F. et. al. Stable Heteroaromatic Carbenes of the Benzimidazole and 1,2,4-Triazole Series. ARKIVOC. 2005, N 8: 10-43.
22. Korotkih M.I., Kysel'ov A.V., Rajenko G.F. ta in. Porivnjal'na ocinka stabilizacii' kon’jugovanyh i aromatychnyh spoluk za ental'pijamy izodesmichnyh reakcij. Praci nauk. tov. im. T.G. Shevchenko, Ser. Himija. 2008, T. 21: 7-63 [in Ukrainian].
23. Korotkih N.I., Glinjanaja N.V., Raenko G.F., Shvajka O.P. Stabil'nye azol'nye karbeny v organicheskom sinteze. Stat'ja v monografii «Himija i biologicheskaja aktivnost' azolov (izbrannye obzory)» pod red. V. Brovarec, V. Zjabrev. LAP Lambert Academic Publishing, 2014 [in Russian].
24. Korotkikh N.I., Glinyanaya N.V., Cowley A.H. et. al. Tandem transformations of 1,2,4-triazol-5-ylidenes into 5-amidino-1,2,4-triazoles. ARKIVOC. 2007, N 16: 156-172.
25. Shvajka O.P., Korotkih M.I. Karbenovi variacii' klasychnyh reakcij. Zhurn. organ. farm. him. 2013, T. 11, 4(44): 3–14 [in Ukrainian].
26. Korotkikh N.I., Cowley A.H., Moore J.A. et. al. Reaction of 1-tert-Butyl-3,4-Diphenyl-1,2,4-Triazol-5-ylidenes with a Malonic Ester. Org. Biomol. Chem. 2008, N 1: 195-199.
27. Glynjana N.V. Syntez ta peretvorennja stabil'nyh karbeniv rjadu 1,2,4-tryazolu. Dys. kand. him. nauk. Donec'k, 2011 [in Ukrainian].
28. Kyselev A.V. Syntez geteroaromatychnyh biskarbeniv rjadu 1,2,4-tryazolu ta novi shljahy otrymannja karbenovyh kompleksiv perehidnyh metaliv. Dys. kand. him. nauk. Donec'k, 2007 [in Ukrainian].
29. Korotkih M.I., Rajenko G.F., Shvajka O.P. Nova versija reakcii' Lejkarta–Vallaha. Avtovidnovlennja formiativ benzimidazoliju do 2N-benzimidazoliniv. Dop. NAN Ukrai'ny. 2001, N 11: 130-133 [in Ukrainian].
30. Korotkikh N.I., Saberov V.Sh., Kiselev A.V. et. al. Heterocyclic carbene complexes of nickel, palladium, and copper(I) as effective catalysts for the reduction of ketones. Chem. Heter. Comp. 2012, 47(12): 1551-1560.
31. Korotkikh N.I., Saberov V.Sh., Glinyanaya N.V. et. al. Catalysis of organic reactions by carbenes and carbene complexes. Chem. Het. Comp. 2013, 49(1): 19-38.
32. Marichev K.O., Korotkih M.I., Kysel'ov A.V. ta in. Karbenovyj kataliz reakcii' transesteryfikacii'. Dop. NAN Ukrai'ny. 2011, N 7: 133-137 [in Ukrainian].
33. Pat. Ukrai'ny 68789. A. Karbeny. Korotkih M.I., Marichev K.O., Kysel'ov A.V., Knishevyc'kyj A.V., Glynjana N.V., Popov A.F., Shvajka O.P. [in Ukrainian].
34. Sabjerov V.Sh., Korotkih M.I., Glynjana N.V. ta in. Kataliz vidnovnogo dehloruvannja p-dyhlorbenzenu karbenovymy kompleksamy paladiju. Dop. NAN Ukrai'ny. 2013, N 2: 112-117 [in Ukrainian].
35. Pat. Ukrai'ny # 77420. Karbenovi kompleksy paladiju. Korotkih M.I., Sabjerov V.Sh., Glynjana N.V., Kysel'ov A.V., Popov A.F., Shvajka O.P. [in Ukrainian].
36. Saberov V.Sh., Evans D.A., Korotkikh N.I. et. al. Exceptionally Efficient Catalytic Hydrodechlorination of Persistent Organic Pollutants: Application of New Sterically Shielded Palladium Carbene Complexes. Dalton Trans. 2014, 43(43): 18117-18122.
37. Glinyanaya N.V., Saberov V.Sh., Korotkikh N.I. et. al. Syntheses of sterically shielded stable carbenes of the 1,2,4-triazole series and their corresponding palladium complexes: efficient catalysts for chloroarene hydrodechlorination. Dalton Trans. 2014, 43(43): 16227-16237.
38. Pat. Ukrai'ny # 62301. A. Karbenovi kompleksy perehidnyh metaliv. Korotkih M.I., Sabjerov V.Sh., Kysel'ov A.V., Marichev K.O., Glynjana N.V., Shvajka O.P. [in Ukrainian].
39. Korotkih M.I., Marichev K.O., Kysel'ov A.V., Shvajka O.P. Syntez pohidnyh kraunkarbenoi'div. Ukrainica bioorganica acta. 2008, 6(2): 22–27 [in Ukrainian].
40. Korotkih M.I., Shvajka O.P., Kysel'ov A.V. ta in. Antymikrobna aktyvnist' proto- ta metalokarbenovyh spoluk rjadu azoliv i azyniv. Visnyk nac. universytetu «L'vivs'ka politehnika». 2008, N 622: 3-6 [in Ukrainian].
41. Kysel'ov A.V., Knishevyc'kyj A.V., Rajenko G.F. ta in. Cyntez ta antybakterial'na aktyvnist' dejakyh aromatychnyh pohidnyh azoliv. Zhurn. organ. farm. him. 2009. T.7, v.1(25): 59-63 [in Ukrainian].
42. Marichev K.O., Glynjana N.V., Korotkih M.I. ta in. Antymikrobna aktyvnist' proto- ta metalokarbenovyh spoluk rjadu azoliv i pirydynu. Zhurn. organ. farm. him. 2011. T. 9, v. 3(35): 72-79 [in Ukrainian].
43. Sabjerov V.Sh., Marichev K.O., Korotkih M.I. ta in. Syntez i antymikrobna aktyvnist' prekarbenovyh ta metalokarbenovyh spoluk rjadu imidazolu. Zhurn. organ. farm. him. 2014. T. 12, v. 2 (46): 36-43 [in Ukrainian].
44. Glynjana N.V., Sabjerov V.Sh., Knishevyc'kyj A.V. ta in. Syntez i antymikrobna aktyvnist' metalokarbenovyh spoluk rjadu tryazoliv. Zhurn. organ. farm. him. 2014. T. 12, v. 2 (46): 44-52.