A mechanistic investigation of anti-elimination in (Z)-1,2-bis(arylseleno)-1-alkenes and their sulfur analogs

作者：Tarao Asami; Tabuchi Yukako; Sugimoto Eri; Ikeda Miki; Uchimoto Hitomi; Arimitsu Kenji; Kimura Hiroyuki; Kawasaki Ikuo; Kawahata Masatoshi; Yamaguchi Kentaro; Nishide Kiyoharu^*

来源：Organic and Biomolecular Chemistry, 2015, 13(21): 5964-5971.

DOI：10.1039/c5ob00490j

The oxidation of (Z)-1,2-bis(arylseleno)-1-alkenes is known to afford alkynyl selenoxides via a unique selenoxide anti-elimination mechanism; however, to date, there have been no mechanistic studies of this reaction. During our studies of this transformation, monoselenoxides 6 and 7 were unexpectedly isolated as stable reaction intermediates. In addition, Se-77 NMR studies of the reaction mixture revealed the presence of an intramolecular Se. O interaction and the formation of alkynyl selenoxides. Meanwhile, even at higher temperatures, the reaction of a (Z)-1,2-bis(arylsulfinyl)-1-alkene, the sulfur analog of (Z)-1,2-bis( arylseleninyl)-1-alkenes, did not proceed via sulfoxide elimination but proceeded via isomerization and disproportionation. Therefore, the intramolecular Se. O interaction can be concluded to play a pivotal role in the anti-elimination reaction.

• 出版日期2015