Reevaluating ortho-Carborane Synthesis: Success with Mono-Substituted Acetylenes in the Presence of Silver Salts

Oleh V. Svaliavyn; Artem M. Mishchenko; Yulian L. Lishchenko; Andrey P. Mityuk; Alona S. Cherednichenko; Nataliya A. Shtil; Volodymyr V. Turcheniuk; Radomyr V. Smaliy; Yuliya V. Rassukana; Olexandr Ye. Pashenko

doi:10.24959/ophcj.24.316200

Authors

Oleh V. Svaliavyn Institute of Organic Chemistry of the National Academy of Sciences of Ukraine; Enamine Ltd., Ukraine https://orcid.org/0009-0004-0692-691X
Artem M. Mishchenko Enamine Ltd., Ukraine
Yulian L. Lishchenko Enamine Ltd., Ukraine
Andrey P. Mityuk Enamine Ltd.; Taras Shevchenko National University of Kyiv, Ukraine https://orcid.org/0009-0009-0303-0508
Alona S. Cherednichenko Institute of Organic Chemistry of the National Academy of Sciences of Ukraine, Ukraine https://orcid.org/0009-0001-7159-6898
Nataliya A. Shtil Institute of Organic Chemistry of the National Academy of Sciences of Ukraine; Enamine Ltd., Ukraine https://orcid.org/0000-0002-3752-898X
Volodymyr V. Turcheniuk Enamine Ltd., Ukraine
Radomyr V. Smaliy Enamine Ltd.; National Technical University of Ukraine “Igor Sikorsky Kyiv Polytechnic Institute”, Ukraine https://orcid.org/0000-0003-0379-1138
Yuliya V. Rassukana Institute of Organic Chemistry of the National Academy of Sciences of Ukraine, Ukraine https://orcid.org/0000-0003-3101-9911
Olexandr Ye. Pashenko Enamine Ltd; Taras Shevchenko National University of Kyiv; Institute of Organic Chemistry of the National Academy of Sciences of Ukraine, Ukraine https://orcid.org/0000-0001-6157-0785

DOI:

https://doi.org/10.24959/ophcj.24.316200

Keywords:

ortho-carborane, decaborane, acetylenes, silver, synthesis

Abstract

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.

Supporting Agency

The work was supported by National Research Foundation of Ukraine (grant No. 0123U104256).

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