The Catalytic Intermolecular Orthoarylation of Phenols

Abstract

The use of Wilkinson's catalyst with diisopropylphosphinite ligands acting as cocatalysts allows the catalytic orthoarylation of phenols [Eq. (1)], a process that relies on a CH activation of a phenol that has been incorporated into the cocatalyst by transesterification.

Nickel-Catalyzed Biaryl Coupling of Heteroarenes and Aryl Halides/Triflates

“…4 The importance of such processes is also connected with an apparent significance of catalytic C-H bond functionalization in chemical synthesis. 5 Indeed, this quest has been the driving force behind enormous efforts in the synthetic community including our group, 6 culminating in a wealth of useful catalytic systems employing Pd, 7 Rh, 8 Ru, 9 and Ir 10 for the C-H bond arylation of heteroarenes with aryl electrophiles. 11…”

Organometallics aspects of C–H bond activation/functionalization

“…The important feature of this methodology is the remarkably mild reaction conditions and excellent functional group tolerance. [73][74][75][76][77] In a recent report the application of a strong paccepting ligand P[(OCH(CF 3 ) 2 ) 3 ] proved viable for the rhodium-catalyzed direct arylations of unactivated arene 46 under microwave irradiations. 78,79 The absence of coordinating moiety resulted in a mixture of ortho-48 and para-substituted 49 regioisomers (Scheme 10), which suggested that an electrophilic aromatic substitution type-mechanism was operative.…”

Catalytic Methods for CH Bond Functionalization: Application in Organic Synthesis

“…(51). [103] The significant point of this reaction is the use of phosphinite as a co-catalyst. The phosphorus atom coordinates to the rhodium atom, then electrophilic substitution with the rhodium(III) species occurs at the ortho position.…”