74525-40-9Relevant articles and documents
Synthesis of aryl ethers from benzoates through carboxylate-directed C-H-activating alkoxylation with concomitant protodecarboxylation
Bhadra, Sukalyan,Dzik, Wojciech I.,Goo?en, Lukas J.
, p. 2959 - 2962 (2013)
One in, one out: In the presence of a copper/silver bimetallic catalyst system, aromatic carboxylate salts undergo ortho C-H alkoxylation with concomitant loss of the carboxylate directing group in a protodecarboxylation step (see scheme, FG=functional group). This process provides a convenient synthetic access to the important class of aromatic ethers from widely available carboxylic acids. Copyright
Biaryl and aryl ketone synthesis via Pd-catalyzed decarboxylase coupling of carboxylate salts with aryl triflates
Goossen, Lukas J.,Linder, Christophe,Rodriguez, Nuria,Lange, Paul P.
supporting information; experimental part, p. 9336 - 9349 (2010/04/03)
A bimetallic catalyst system has been developed that for the first time allows the decarboxylative crosscoupling of aryl and acyl carboxylates with aryl triflates. In contrast to aryl halides, these electrophiles give rise to non-coordinating anions as byproducts, which do not interfere with the decarboxylation step that leads to the generation of the carbon nucleophilic crosscoupling partner. As a result, the scope of carboxylate substrates usable in this transformation was extended from ortho-substituted or otherwise activated derivatives to a broad range of ortho-, meta-, and para-substituted aromatic carboxylates. Two alternative protocols have been optimized, one involving heating the substrates in the presence of CuI/1,10- phenanthroline (10-15 mol %) and PdI2/phosphine (23 mol%) in NMP for 1-24 h, the other involving CuI/l,10-phenanthroline (615mol%) and PdBr2/Tol-BINAP (2 mol % ) in NMP using microwave heating for 5-10 min. While most products are accessible using standard heating, the use of microwave irradiation was found to be beneficial especially for the conversion of non-activated carboxylates with functionalized aryl triflates. The synthetic utility of the transformation is demonstrated with 48 examples showing the scope and limitations of both protocols. In mechanistic studies, the special role of microwave irradiation is elucidated, and further perspectives of decarboxylase crosscouplings are discussed.
