Ruthenium-Catalyzed S-Propargylation of Thiols Enables the Rapid Synthesis of Propargylic Sulfides
Teruyuki Kondo, Yusuke Kanda, Atsushi Baba, Kenji Fukuda, Ayako Nakamura, Kenji Wada, Yasuhiro Morisaki, and Take-aki Mitsudo*
*Department of Energy and Hydrocarbon Chemistry, Graduate School of
Engineering, Kyoto University, Sakyo-ku, Kyoto 606-8501, Japan, Email: mitsudo
scl.kyoto-u.ac.jp
T. Kondo, Y. Kanda, A. Baba, K. Fukuda, A. Nakamura, K. Wada, Y. Morisaki, T.-A. Mitsudo, J. Am. Chem. Soc., 2002, 124, 12960-12961.
DOI: 10.1021/ja027750o
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Abstract
A ruthenium-catalyzed S-propargylation of thiols by propargylic carbonates under neutral conditions, in which specific requirements inherent to the different reactivities of aliphatic and aromatic thiols was achieved by tuning both the nature of the ligands and the experimental conditions.
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Details
The document discusses the development of a novel ruthenium-catalyzed S-propargylation of thiols, enabling the rapid synthesis of propargylic sulfides. Propargylic sulfides are biologically active compounds and useful in synthesizing sulfur-containing monomers. The research, conducted by Teruyuki Kondo and colleagues at Kyoto University, addresses the challenge of catalyst poisoning by organosulfur compounds. The team found that CpRuCl(cod) and CpRuCl(PPh3)2 are effective catalysts for the reaction, with N-methylpiperidine serving as a suitable solvent and ligand. The reaction proceeds under neutral conditions and elevated temperatures, yielding high amounts of propargylic sulfides from aromatic thiols and internal propargylic carbonates. However, CpRuCl(cod) was ineffective for aliphatic thiols, for which CpRuCl(PPh3)2 was found to be effective. The reaction mechanism likely involves a (σ-propargyl)ruthenium intermediate. This new method complements previous thiolato-bridged diruthenium complex-catalyzed reactions and opens new opportunities in transition-metal complex-catalyzed sulfur chemistry. The research was supported by various Japanese scientific foundations and provides a significant advancement in the field of catalytic synthesis of sulfur-containing compounds.
Key Words
ID: J48-Y2002-1330
