Transition Metal-Free Acetylene Chemistry: Trends and Rates of Development. A Review

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Abstract

Behind the modern snowballing growth of publications devoted to transition metal-catalyzed chemistry of acetylene, the works dealing with acid- and base-promoted acetylene reactions stand in the background, although acid-base catalysis, along with enzymatic one, hold a dominant place in living nature. It was acid-base catalysis that was historically first introduced into human practice, and then into research. Until now, the majority of practically important reactions involving acetylene (these are mainly Favorsky reactions: vinylation of alcohols, ethynylation of carbonyl compounds, prototropic isomerization of alkynes, rearrangement of α-haloketones) represent base-catalyzed processes. Over the last decades, transition metal-free acetylene chemistry was progressing owing to the employment of superbases and superacids for the activation of the triple carbon–carbon bond. In the present paper, using recent publications of the authors (2021), the advances in application of superbase media in the chemistry of alkynes are surveyed. Also, the usage of electron-deficient acetylenes as objects especially sensitive to the action of bases in the search for new preparative reactions with participation of the triple carbon–carbon bond is analyzed. A short period (one year) was chosen in order to clearly illustrate the dynamics and efficiency of research in this area.

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About the authors

E. Yu. Schmidt

Favorsky Irkutsk Institute of Chemistry of the Siberian Branch of the Russian Academy of Sciences

Email: boris_trofimov@irioch.irk.ru
Russian Federation, Irkutsk

B. A. Trofimov

Favorsky Irkutsk Institute of Chemistry of the Siberian Branch of the Russian Academy of Sciences

Author for correspondence.
Email: boris_trofimov@irioch.irk.ru

Academician of the RAS

Russian Federation, Irkutsk

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Supplementary files

Supplementary Files
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1. JATS XML
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2. Scheme 1. Single-reactor synthesis of diaminoketones 1 [2].

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3. Scheme 2. Putative mechanism for the formation of diaminoketones 1.

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4. Scheme 3. Cyclisation of diaminoketones 1 into hexahydropyrrolo[3,2-b]indoles 2 [2].

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5. Scheme 4. Putative mechanism of formation of hexahydropyrrolo[3,2-b]indoles 2.

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6. Scheme 5. Cyclisation of diaminoketones 1 to pyrrolidines 3 [2].

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7. Scheme 6. Putative mechanism of formation of pyrrolidines 3.

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8. Scheme 7. Synthesis of benzylidenpiperidinols [2].

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9. Scheme 8. Two-step synthesis of N-(arylamino)thieno[3,2-b]pyrroles [10].

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10. Scheme 9. Putative mechanism for the transformation of 7-methylene-6,8-dioxabicyclo[3.2.1.1]octanes 6 into N-(aryl-amino)thieno[3,2-b]pyrroles 7.

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11. Scheme 10. Synthesis of 1-pyrrolines and 2H-pyrroles [14].

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12. Scheme 11. Suggested mechanism of formation of 2,3,5-triaryl-1-pyrrolines and polyarylated 2H-pyrroles [14].

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13. Scheme 12. One-step synthesis of 2,4,6-triarylpyridines 11 [21].

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14. Scheme 13. Suggested mechanism of formation of 2,4,6-triarylpyridines 11.

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15. Scheme 14. Hydroamination of acylethynylpyrroles [30].

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16. Scheme 15. Synthesis of pyrrolylacylpyridines [30].

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17. Scheme 16. Suggested mechanism of formation of pyrrolylacylpyridines.

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18. Scheme 17. Synthesis of E,Z-pyrrolylaminodienediones [30].

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19. Scheme 18. Synthesis of 3-(acyl)-5-(acyl ethenyl)pyrrolylpyridines [30].

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20. Scheme 19. Putative mechanism for the formation of 3-(acyl)-5-(acyl ethenyl)pyrrolylpyridines.

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21. Scheme 20. Double functionalisation of quinolines with cyanoacetylenes [32].

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22. Scheme 21. Assumed mechanism of double functionalisation of quinolines [32].

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23. Scheme 22. Synthesis of furo[3,4-b]quinolinones [32].

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24. Scheme 23. Hydrolysis of 2-acetal-3-cyanoquinolines [32].

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25. Scheme 24. Synthesis of 2-sulfanyl-3-(ferrocenylmethoxy)-1H-pyrroles and their rearrangement into 2-(ferrocenylmethyl)-1,2-dihydro-3H-pyrrol-3-ones [34].

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