Remote Stereocontrol in the Synthesis of Acyclic 1,4-Diols and 1,4‑Aminoalcohols from 2‑Sulfinyl Dienes

The highly diastereoselective conjugate
addition of alcohols and
amines (RXH) to enantiopure 2-sulfinyl dienes renders transient allylic
sulfoxides which undergo sulfoxide–sulfenate rearrangement
and sulfenate cleavage providing 2-ene-1,4-diols and 2-ene-1,4-aminoalcohols
with up to 99:1 dr. The method allows for the generation of two stereocenters
in a single synthetic operation with remote chirality transfer of
one center into the other.