Copper‐Mediated CH/CH Biaryl Coupling of Benzoic Acid Derivatives and 1,3‐Azoles

Abstract

Hot couple: A precious‐metal‐free copper‐mediated intermolecular direct biaryl coupling of benzoic acid derivatives and 1,3‐azoles has been developed. The key to success is the installation of an amide‐based bidentate coordinating group, which is easily removed and transformed into the parent ester groups after the coupling reaction. Kinetic studies indicate that the rate‐limiting step is the aromatic CH bond cleavage of benzoic acid derivatives.

Copper-Mediated Intermolecular C–H/C–H and C–H/N–H Couplings via Aromatic C–H Cleavage

“…The related dehydrogenative biaryl couplings of indoles, benzamides, and naphthylamines also proceed in the presence of Cu(OAc) 2 , with the assistance of appropriate directing groups, to make the corresponding bi(hetero)aryl linkages efficiently (Eqs. 15-17) [35][36][37]. The directors except for the 2-phenylpyridine are readily attachable and detachable: 2-pyrimidyl (Eq.…”

Katalytische Funktionalisierung von C(sp2)‐H‐ und C(sp3)‐H‐Bindungen unter Verwendung von zweizähnigen dirigierenden Gruppen

“…Ein Kupfersalz vermittelte die C(sp 2 )-H/C(sp 2 )-HKupplung von Benzoesäurederivaten und 1,3-Azolen, wenn das Substrat eine zweizähnige dirigierende 8-Aminochinolingruppe aufwies (Schema 41). [59] Elektronisch und sterisch unterschiedliche Substituenten der Amidderivate in o-, mund p-Stellung werden toleriert. Substrate, die zwei potenziell C-H-Funktionalisierung zweizähnigen dirigierenden Gruppen, zu katalytischen Reaktionen zu gelangen.…”

Enantioselective Construction of Acyclic Quaternary Carbon Stereocenters: Palladium-Catalyzed Decarboxylative Allylic Alkylation of Fully Substituted Amide Enolates

“…Activated amides are among the most widely utilized carboxyllic acid derivatives and have seen historical synthetic use 16 as well as more recent applications in catalytic transformations. 17 Additionally, we surmised that having the ability to tune the electronic and steric nature of the amido functionality would be critical for the success of the asymmetric catalysis. Thus, based on our past experience with catalytic enantioselective allylic alkylations of lactam-derived enolates, we intentionally focused our studies on amido-type enolate chemistry.…”