Synthesis of planar chiral pseudo–ortho-substituted aryl[2.2]paracyclophanes by stepwise successive palladium-catalyzed coupling reactions

Planar chiral aryl[2.2]paracyclophanyl-thioureas and -phosphine with a pseudo–ortho substitution pattern have been designed and efficiently synthesized by stepwise successive palladium-catalyzed cross-coupling reactions.

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(Sp)-12-Bromo[2.2]paracyclophan-4-yl trifluoromethanesulfonateC17H14O3F3SBr[α]D26=+35.9 (c 1.00, CHCl3)Source of chirality: (S)-camphanoyl chlorideAbsolute configuration: (Sp)

(Sp)-12-Amino[2.2]paracyclophan-4-yl trifluoromethanesulfonateC17H16F3NSO3[α]D25=-22.0 (c 1.00, CHCl3)Source of chirality: (S)-camphanoyl chlorideAbsolute configuration: (Sp)

(Sp)-5-(12-Amino[2.2]paracyclophan-4-yl)resorcinolC22H21O2N[α]D26=-93.7 (c 0.96, MeOH)Source of chirality: (S)-camphanoyl chlorideAbsolute configuration: (Sp)

(Sp)-N-[3,5-Bis(trifluoromethyl)phenyl]-N′-{12-(3,5-dihydroxyphenyl)[2.2]paracyclophan-4-yl}thioureaC31H24F6N2O2S[α]D25=-211.5 (c 0.30, CHCl3)Source of chirality: (S)-camphanoyl chlorideAbsolute configuration: (Sp)

(Sp)-12-(3,5-Dimethoxyphenyl)[2.2]paracyclophan-4-yl trifluoromethanesulfonateC25H23F3O5S[α]D23=-58.8 (c 1.00, CHCl3)Source of chirality: (S)-camphanoyl chlorideAbsolute configuration: (Sp)

(Sp)-{12-(3,5-Dimethoxyphenyl)[2.2]paracyclophan-4-yl}diphenylphosphine oxideC36H33O3P[α]D24=-41.1 (c 1.00, CHCl3)Source of chirality: (S)-camphanoyl chlorideAbsolute configuration: (Sp)

(Sp)-{12-(3,5-Dihydroxyphenyl)[2.2]paracyclophan-4-yl}diphenylphosphineC34H29O2P[α]D20=-113.8 (c 0.81, CHCl3)Source of chirality: (S)-camphanoyl chlorideAbsolute configuration: (Sp)