A palladium-catalyzed carbonylative approach for the direct conversion of (hetero)aryl bromides into their α,α-bis(trifluoromethyl)carbinols is described, and it employs only stoichiometric amounts of carbon monoxide and trifluoromethyltrimethylsilane. In addition, aryl fluorosulfates proved highly compatible with these reaction conditions. The method is tolerant of a diverse set of functional groups, and it is adaptable to late-stage carbon-isotope labeling.
We report on an efficient Ir-catalyzed decarbonylation of glycerol, which could be coupled to an ensuing Pdcatalyzed alkoxycarbonylation of styrenes. The formation of hydrogen could be avoided by employing 1,4-benzoquinone (BQ) as an external oxidant. A wide variety of styrenes underwent the esterification in good yields and high regioselectivity. Applying catalytic amounts of hexafluoroisopropanol provided access to alcohols other than methanol, which this transformation is often limited to. Finally, we demonstrate the suitability of this methodology for the preparation of three well-known nonsteroidal anti-inflammatory drugs (NSAIDs).
Ap alladium-catalyzed carbonylative approachf or the direct conversion of (hetero)aryl bromides into their a,abis(trifluoromethyl)carbinols is described, and it employs only stoichiometric amounts of carbon monoxide and trifluoromethyltrimethylsilane.I na ddition, aryl fluorosulfates proved highly compatible with these reaction conditions.T he method is tolerant of ad iverse set of functional groups,a nd it is adaptable to late-stage carbon-isotope labeling.
Conflict of interestTr oels Skrydstrup is ac o-owner of SyTracks a/s,w hich commercializes COgen and the two-chamber technology.
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