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Updated: Jun 20, 2025

Preparation of N-2-alkoxyvinylsulfonamides from N-tosyl-1,2,3-triazoles and Subsequent Conversion to Substituted Phthalans and Phenethylamines
Published on: January 3, 2018
Metal-catalyzed valence isomerization of a methylene(thioxo)phosphorane to a thiaphosphirane
Shintaro Ishida1, Yusuke Yoshida1, Takeaki Iwamoto1
1Department of Chemistry, Graduate School of Science, Tohoku University, Aoba-ku, Sendai 980-8578, Japan. ishida@tohoku.ac.jp.
Abstract:
We explored coordination chemistry associated with valence isomerization between a methylene(thioxo)phosphorane (MTP) and a thiaphosphirane. For this purpose, we developed the selective synthesis of a MTP by eliminating chlorodimethylphenylsilane from the corresponding chlorophosphine sulfide. Treatment of the MTP with an equivalent amount of pentafluorophenylgold(I) complex resulted in the formation of a thiaphosphirane gold(I) complex, which likely proceeds via an η2-P,C-MTP gold complex. The MTP undergoes a valence isomerization catalyzed by copper(I) chloride to furnish a transition metal-free thiaphosphirane. Computational studies proposed a plausible mechanism involving a Cu-assisted cyclization reaction.
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