Palladium-Catalyzed Addition and Carbonylative Addition of Diaryl Disulfides and Diselenides to Terminal Acetylenes

Hitoshi Kuniyasu, Akiya Ogawa*, Shin Ichiro Miyazaki, Ilhyong Ryu, Nobuaki Kambe, Noboru Sonoda

*Corresponding author for this work

Research output: Contribution to journalArticle

238 Scopus citations

Abstract

Novel transition-metal-catalyzed reactions of disulfides and diselenides with acetylenes are described. In the presence of tetrakis(triphenylphosphine)palladium(0), [Pd(PPh3)4], the (1) of diaryl disulfides and diselenides to terminal acetylenes 1 takes place stereoselectively to give high yields of (Z)-l,2-bis(arylthio)-l-alkenes 2 and (Z)-l,2-bis(arylseleno)-l-alkenes 3, respectively. A mechanistic proposal includes the following: (1) oxidative addition of (ArY)2 [Y = S, Se] to low-valent palladium species, (2) stereoselective cis-thiopalladation or cis-selenopalladation to acetylenes to form a cis-vinylpalladium intermediate, and (3) reductive elimination of the product with retention of the stereochemistry. When the reaction of diaryl disulfides and diselenides with terminal acetylenes is performed under the pressure of carbon monoxide, the carbonylative addition occurs to afford (Z)-l,3-bis(arylthio)-2-alken-l-ones 4 and (Z*)-l,3-bis(arylseleno)-2-alken-l-ones 5, respectively. Carbon monoxide is regioselectively incorporated on the side of the terminal carbon of the acetylenes.

Original languageEnglish
Pages (from-to)9796-9803
Number of pages8
JournalJournal of the American Chemical Society
Volume113
Issue number26
DOIs
StatePublished - 1 Dec 1991

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