Pd-catalyzed asymmetric allylic aminations with aromatic amine nucleophiles using chiral diaminophosphine oxides: DIAPHOXs

Asymmetric allylic aminations with aromatic amine nucleophiles using Pd–DIAPHOX catalyst systems are described. The asymmetric allylic aminations of various allylic carbonates proceeded using 2–5 mol % of the catalyst and BSA, providing the corresponding N-aryl chiral allylic amines in up to 99% ee for cyclic substrates, and in up to 97% ee for acyclic substrates.

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(6S)-6-(4-Methoxy-phenylamino)-cyclohex-1-enecarboxylic acid methyl esterC15H19NO3Ee = 94%[α]D20=-98.2 (c 0.62, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (S)

(1S)-(4-Methoxy-phenyl)-2-phenyl-cyclohex-2-enyl)-amineC19H21NOEe = 97%[α]D23=-165.4 (c 0.14, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (S)

(1R)-(1,3-Diphenyl-allyl)-(4-methoxy-phenyl)-amineC22H21NOEe = 97%[α]D22=-56.2 (c 0.80, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (R)