Decarbonylative Sonogashira Cross-Coupling of Carboxylic Acids
Chengwei Liu, Michal Szostak
Abstract
Decarbonylative Sonogashira cross-coupling of carboxylic acids by palladium catalysis is presented. The carboxylic acid is activated in situ by the formation of a mixed anhydride and further decarbonylates using the Pd(OAc)2/Xantphos system to provide an aryl–Pd intermediate, which is intercepted by alkynes to access the traditional Pd(0)/(II) cycle using carboxylic acids as ubiquitous and orthogonal electrophilic cross-coupling partners. The methodology efficiently constructs new C(sp2)–C(sp) bonds and can be applied to the derivatization of pharmaceuticals. Mechanistic studies give support to decarbonylation preceding transmetalation in this process.
Topics & Concepts
ChemistryTransmetalationDecarbonylationSonogashira couplingXantphosCarboxylic acidArylPalladiumDerivatizationCarbodiimideCombinatorial chemistryElectrophileOrganic chemistryCatalysisHigh-performance liquid chromatographyAlkylCatalytic Cross-Coupling ReactionsCatalytic C–H Functionalization MethodsOrganoboron and organosilicon chemistry