jo0006977_si_001.pdf (721.57 kB)
Download file

Unique Regio- and Stereoselectivity in Pd-Catalyzed Chlorocarbonylation Reaction of 2-Phenylethynyl Selenides and 2-Alkylethynyl Selenides. Highly Stereoselective Synthesis of 2-Seleno-3-chloroacrylates

Download (721.57 kB)
journal contribution
posted on 01.09.2000, 00:00 authored by Xian Huang, Aiming Sun
Regio- and stereoselectivity in the chloropalladation carbonylation reaction of different acetylenic selenides in the presence of 0.05 equiv of PdCl2 and 3 equiv of cupric chloride under 1 atm of carbon monoxide affording 2-seleno-3-chloroacrylates were investigated. Opposite stereoselectivities were observed with 2-phenylethynyl selenides and 2-alkylethynyl selenides:  the reactions of 2-phenylethynyl selenides afforded (E)-2-seleno-3-chloro-3-phenylacrylates, while the reactions of 2-alkylethynyl selenides gave (Z)-2-seleno-3-chloro-3-alkylacrylates. A chloropalladation carbonylation mechanism for this reaction was proposed. The regio- and stereoselective chloropalladation of the carbon−carbon triple bond in acetylenic selenides affords 1-enylpalladium intermediates, in which the palladium atom connects with the carbon atom bonding with the selenium atom. Carbonylation in the presence of an alcohol affords 2-seleno-3-chloroacrylates.

History