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Competitive Carbothiolation and Sonogashira Cross‐Coupling in the Reaction of Trimethylsilylacetylene with Arylthioacetates
Author(s) -
Iovine Valentina,
Cruciani Federico,
Picini Flavio,
Varrone Marta,
Rossi Enrico,
Bassetti Mauro,
D'Annibale Andrea
Publication year - 2016
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.201601373
Subject(s) - sonogashira coupling , chemistry , halide , medicinal chemistry , triple bond , oxidative addition , aryl , palladium , catalysis , organic chemistry , double bond , alkyl
p ‐Bromo‐ or p ‐iodophenylthioacetate can react with trimethylsilylacetylene by simultaneous Sonogashira coupling at the halide function and addition of acetyl and arylthio moieties to the triple bond. Reaction of arylthioacetates with p ‐OMe, ‐Me, Ph and ‐Cl substituents, under the typical conditions of the Sonogashira coupling, leads only to the regio‐ and stereoselective acetylthiolation of trimethylsilylacetylene affording β‐silylated‐β‐arylthio‐α,β‐unsaturated ketones. The carbothiolation of PhSAc is faster than the Sonogashira coupling of Ph−Br and slower than that of Ph−I, implying that the rates of oxidative addition to Pd(0) are in the order (X=I > SAc >Br).