Non-directed Pd-catalysed C–H arylation of [2.2]paracyclophane

Abstract

We report herein the palladium-catalysed mono-selective C–H arylation of [2.2]paracyclophane (PCP) with diverse aryl iodides in the absence of any pendant directing groups, providing a straightforward and modular access to...

Palladium Catalysis: Dependence of the Efficiency of C−C Bond Formation on Carboxylate Ligand and Alkali Metal Carboxylate or Carboxylic Acid Additive. Part A: the C(sp2)−C(sp2), C(sp2)−C(sp3) and C(sp3)−C(sp3) Bonds

“…The Heck reaction of [2.2]paracyclophane with phenyl iodide has been studied using different Pd catalysts and silver carboxylates (Scheme 2l). [26] The best result arose with PdCl 2 (PCy 3 ) 2 and AgOAc in hexafluoroisopropanol, dichloromethane and trifluoroacetic acid leading to lower yields. With this catalyst, no reaction occurred in the absence of the silver salt.…”

Ligand-Enabled C6-Selective C–H Arylation of Pyrrolo[2,3-d] Pyrimidine Derivatives with Pd Catalysts: An Approach to the Synthesis of EGFR Inhibitor AEE-788

“…In particular, C–H activation without using a directing group provides complementary synthetic functionality compared to the widely developed chelation-assisted C–H arylation reaction . Notably, Pd­(II)-catalyzed ligand-promoted nondirected C–H arylation reactions have attracted considerable attention to organic chemists in recent years . However, despite the impressive connections they enable, the synthetic efficiency of these methodologies is limited by requiring excessive amounts of reagents and achieving site selectivity based on electronic and steric effects …”

Synthesis of [2.2]Paracyclophane-Fused Heterocycles via Palladium-Catalyzed C–H Activation/Annulation of [2.2]Paracyclophanecarboxamides with Arynes

“…In the past two decades, transition-metal-catalyzed C–H functionalization has witnessed a booming development, and been successfully employed to access [2.2]­paracyclophane derivatives . Meanwhile, palladium-catalyzed intramolecular C–H activation offers an efficient pathway to afford [2.2]­paracyclophane-fused heterocycles by introducing appropriate coupling partners tethered to the [2.2]­paracyclophane backbone (Scheme b). , Nevertheless, the lower catalytic efficiency due to the constraint by the sterically hindered configuration of the [2.2]­paracyclophane skeleton and the limited types of the tethering coupling partners restrict their further applications.…”