The Synthesis of Chiral β,β-Diaryl Allylic Alcohols and Their Use in the Preparation of α-Tertiary Allylamines and Quaternary α-Amino Acids.

Abstract

An approach to nonracemic β,β-diarylsubstituted allyl alcohols is described. Their synthesis starts from l-lactic acid-derived propargyl alcohol, which is submitted to sequential Sonogashira/Suzuki or Sonagashira/Stille coupling reactions. Both approaches enable the synthesis of either (Z)- or (E)-allylic alcohols regarding the order of introducing coupling agents. The obtained allyl alcohols were applied in the synthesis of nonracemic α-tertiary allylamines via stereocontrolled cyanate-to-isocyanate sigmatropic rearrangement reactions of the corresponding allyl carbamates. The stereoselectivity of the process is controlled by the geometry of the double bond of the starting allyl derivative. As demonstrated, a rearrangement of (S,Z)-allyl carbamates provides (S)-teriary allylamines, whereas the transformation (S,E)-isomers leads to (R)-allylamines.