Перегляд синтезу орто-карборанів: успіх для монозаміщених ацетиленів у присутності солей срібла

• Date: 2024
• Main Authors: Svaliavyn, Oleh V., Mishchenko, Artem M., Lishchenko, Yulian L., Mityuk, Andrey P., Cherednichenko, Alona S., Shtil, Nataliya A., Turcheniuk, Volodymyr V., Smaliy, Radomyr V., Rassukana, Yuliya V., Pashenko, Olexandr Ye.
• Format: Article
• Language: English
• Published: National University of Pharmacy 2024
• Subjects: орто-карборани; декаборан; ацетилени; срібло; синтез
• Online Access: https://ophcj.nuph.edu.ua/article/view/316200
• Journal Title: Journal of Organic and Pharmaceutical Chemistry

The study shows that traditional methods for synthesizing ortho-carboranes from nido-B10H14 and its complexes (B10H12L2) using donor- and acceptor-disubstituted acetylenes yielding low efficiencies (yields 0 - 12%). Attempts to improve yields with ionic liquids and silver salts as catalysts were unsuccessful with disubstituted acetylenes. However, it has been found that the use of mono-substituted acetylenes (phenylacetylene, ethyl propiolate) in the presence of silver salts in the reaction with B10H12L2 substrates produces ortho-carboranes in high yields (~90%). This suggests that the key step is the formation and subsequent addition of silver acetylenides, and not the donor-acceptor π-complexes previously assumed. This finding allows us to better understand the mechanisms of the ortho-carboranes formation and offers an efficient pathway for their synthesis.