Ni‐Catalyzed Decarboxylative Cross‐Coupling of Potassium Polyfluorobenzoates with Unactivated Phenol and Phenylmethanol Derivatives

Abstract

A Ni-catalyzed decarboxylative crosscoupling of potassium polyfluorobenzoates with unactivated phenol and phenylmethanol derivatives is described. This novel transformation provides a practical and efficient protocol towards the synthesis of important polyfluorobiaryls and polyfluorinated diarylmethanes, and greatly enlarges the range of electrophiles utilized in decarboxylative coupling. Remarkably, preliminary mechanistic studies indicated the essential role of Zn(OAc) 2 might lie in the enhancement of decarboxylation step.

Development of a Fluorescent Nanofibrous Template by In Situ SNAr Polymerization of Fluorine-Containing Terphenyls with Aliphatic Diols: Self-Assembly and Optical and Liquid Crystal Properties

“…This is a very efficient reaction providing high-quality yields. 29 It has been known that the higher number of fluorines on a phenyl ring results in increasing the reactivity of this aryl moiety toward decarboxylative cross-coupling reactions. On the other hand, decreasing the number of fluorine atoms results in lower reactivity, which requires solvent replacement and extra catalysis, such as dimethyl acetamide as a solvent and Cu(I)/phenanthroline as a catalytic mixture.…”

“…Thus, the fluorine substitution was monitored to considerably enhance the intramolecular charge transfer (ICT). 29 The prepared polyethers composed of an electron-withdrawing fluoroaryl conjugate core moiety bonded to electron-donating terminal aliphatic groups. The electron-withdrawing effect of the fluoroaryl conjugate core was improved with the multiple fluorine substitution on the phenyl rings.…”

“…The high electronegativity of fluorine imparts the carbon–fluorine bond a higher dipole moment compared to that of a carbon–hydrogen bond. 29 The mesogenic phases were studied by DSC and POM. Changing the length of the aliphatic diol chain was recognized as a major factor in changing the liquid crystalline mesogenic phases.…”

Biaryl Construction Based on Nickel-Catalyzed C–O Bond Activation

“…In 2018, Zhang's Group developed a nickel-catalyzed crossdecarboxylation-coupling of potassium poly-fluorobenzoate 233 with phenol and phenylmethanol derivatives 232. 68 This method has good functional group compatibility, various polyfluorinated biaryl and polyfluorinated diaryl methanes can be obtained with moderate to excellent yields. Preliminary mechanism studies indicate that the critical role of Zn(OAc)2 probably be the enhancement of the decarboxylation step, thus improving the reaction efficiency, to form intermediate 236.…”

“…The initial oxidative addition of the C(sp In 2018, Zhang's group developed a nickel-catalyzed cross-decarboxylation-coupling of potassium polyfluorobenzoate 233 with phenol and phenylmethanol derivatives 232. 67 This method has good functional group compatibility, and various polyfluorinated biaryl and polyfluorinated diaryl methanes were obtained in moderate to excellent In 2018, Ong's group reported a Ni(COD) 2 /IPr-catalyzed cross-coupling reaction of benzimidazole 239 and anisoles 238 via a tandem C-H/C-O activation pathway. 68 The key to this simultaneous C-H/C-O bond activation was the use of sterically demanding o-tolylMgBr.…”