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1.2.3.6.1 Addition of Arenethiols to Alkynes To Form Vinyl Sulfides

DOI: 10.1055/sos-SD-001-00206

Takacs, J. M.; Vayalakkada, S.; Jiang, X.Science of Synthesis, (20011304.

Unlike the free-radical and rhodium-catalyzed additions of thiols to alkynes, the palladium-catalyzed additions provide Markovnikov adducts regioselectively. For example, palladium(II) acetate effects the Markovnikov addition of benzenethiol to alkyne 160 to give predominantly vinyl sulfide 161 (Scheme 44).[‌41‌,‌42‌] Hydroxy, trimethylsilyl, and amino groups may be present in the alkyne partner, and an alkyne bearing a tethered alkene moiety undergoes chemoselective addition to the triple bond. Some other divalent palladium complexes, especially bis(benzonitrile)dichloropalladium(II), exhibit excellent catalytic activity for the sequential Markovnikov addition and double bond isomerization to afford the corresponding internal vinyl sulfides 162 selectively. However, substrates bearing a basic amino group or ones that lack a propargylic hydrogen give only the Markovnikov adduct 161.[‌42‌]

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