Lewis Acid Catalyzed Reaction of Methylenecyclopropanes with 1,2-Diphenyldiselane or 1,2-Di-p-tolyldisulfane

Abstract

Catalyzed by Lewis acid, 1,2-diphenyldiselane or 1,2-di-p-tolyldisulfane could add to methylenecyclopropanes smoothly. Compared with the reported free radical additions, the results were quite different. A four-membered carbon ring was constructed to give cyclobutane-1,1-diylbis(phenylselane) derivatives or cyclobutane-1,1-diylbis(p-tolylsulfane) derivatives as products, which are useful intermediates in organic synthesis.

Iron salt, a cheap, highly efficient and environment-friendly metal catalyst for Se–Se bond cleavage and the further reaction with methylenecyclopropanes under mild conditions

“…Recently, we have developed a direct access to 1,1-diphenylselenylcyclobutanes from MCPs through the TiCl 4 catalyzed additions of diphenyldiselenide (Scheme 1, eq. (2)) [42]. Avoidance of benzeneselenol made this method more environment-friendly.…”

Organoselenium‐Catalyzed Oxidative Ring Expansion of Methylenecyclopropanes with Hydrogen Peroxide

“…Electrophilic addition of 3 to MCP 1 leads to intermediate 4 . As the cyclopropylmethylium cation bears a selenium group at the α position, ring expansion of 4 occurs to give intermediate cyclobutyl cation 5 , which affords 6 through intramolecular rearrangement . Decomposition of 6 affords final product 2 and organoseleninic acid 7 , which regenerates catalytic species 3 after oxidation by H 2 O 2 (Scheme ) .…”

Construction of Carbocycles from Methylenecyclopropanes

“…The reaction of 79 with MCPs 1 afforded the unique bisphenylselenylcyclobutanes 80 . With TiCl 4 as catalyst, the reaction was performed at −75 °C to room temperature; When using FeCl 3 as catalyst, the reaction occurred smoothly at room temperature . The reaction could be extended to synthesize other bisphenylthiocyclobutanes…”