Regioselective ortho-Palladation of [2.2]Paracyclophane Scaffolds: Accessing Planar and Central Chiral N,C-Palladacycles

In this report, we describe a series of cyclophanyl-derived mono- and binuclear N,C-palladacycles by regioselective ortho-palladation of amine-functionalized [2.2]paracyclophanes. Employing Pd(OAc)(2) followed by LiCl and with the subsequent modular treatment of Ph3P, Cy3P, and (Ph2PCH2)(2), this strategy allows to prepare stable cyclophanyl-derived planar and central chiral N,C-palladacycles in a highly selective manner. The regioselective ortho-palladation mono- and bimetallic product formation was analyzed by detailed spectroscopic techniques, mass spectrometry and unambiguously confirmed by single-crystal X-ray analysis.

Automated summary

This report describes the synthesis of a series of cyclophanyl-derived mono- and binuclear N,C-palladacycles through regioselective ortho-palladation of amine-functionalized [2.2]paracyclophanes. The formation of planar and central chiral N,C-palladacycles was achieved in a highly selective manner using Pd(OAc)(2) followed by LiCl and modular treatment of different phosphines. The regioselective ortho-palladation mono- and bimetallic products were confirmed by detailed spectroscopic techniques, mass spectrometry, and single-crystal X-ray analysis.