We have developed a concise and efficient synthetic method of planar chiral pseudo-ortho-substituted aryl[2.2]paracyclophane molecules possessing C-H bond donors and/or nucleophilic functional groups through the stepwise successive palladium-catalyzed coupling of 12-bromo[2.2]cyclophan-4-yl triflate. Buchwald-Hartwig amination and subsequent Suzuki-Miyaura coupling, followed by the functional group transformation afforded aryl[2.2]cyclophanyl thiourea derivatives. The combination of Suzuki-Miyaura coupling and phosphinylation delivered arylcyclophanyl phosphines. The catalytic activities of the newly synthesized chiral cyclophanyl-thioureas and -phosphines were evaluated based on the aza-Morita-Baylis-Hillman reaction of N-tosylaldimine and methyl vinyl ketone.
