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1.2.3.6.3 Addition of Diaryl Disulfides to Alkynes To Form 1,2-Disulfanylalkenes

DOI: 10.1055/sos-SD-001-00206

Takacs, J. M.; Vayalakkada, S.; Jiang, X.Science of Synthesis, (20011308.

The palladium-catalyzed reaction of disulfides with terminal alkynes 164 (R2=H) proceeds stereoselectively to give high yields of (Z)-1,2-bis(phenylsulfanyl)alk-1-enes 177 (Scheme 49).[‌46‌] The addition of diphenyl disulfide to alkynes proceeds efficiently with tetrakis(triphenylphosphine)palladium(0). In contrast, palladium(II) complexes do not catalyze the reaction. Certain functional groups, e.g. hydroxy, trimethylsilyl, and amino groups, are tolerated in the reaction. In the case of an enyne substrate, the addition reaction takes place chemoselectively on the triple bond. In contrast to the facile reaction of terminal alkynes, the addition of disulfides to internal acetylenes (e.g., 164, R2=Pr) proceeds poorly.

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