Embedding an allylmetal dimer in a chiral cavity: the unprecedented stereoselectivity of a twofold wittig [1,2]-rearrangement

After alpha,alpha'-dimetalation, both 2,2'-diallyloxy-1,1'-binaphthyl and 2,2'-di-2-methylallyloxy-1,1'-binaphthyl undergo the Wittig rearrangement with perfect diastereoselectivity. When racemic 1,1'-binaphthyl-2,2'-diol ("BINOL") is used as the starting material, it gives rise to a 1:1 mixture of antipodal stereoisomers, whereas enantiomerically pure (M)-2,2'-diallyloxy-1,1'-binaphthyl affords (M)-(S,S)-1,1-(1,1'-binaphthyl-2,2'-diyl)bis(2-propen-1-ol) as the sole product. The (M)-(S,S)/(P)-(R,R) mixture resulting from the rearrangement of racemic 2,2'-diallyloxy-1,1'-binaphthyl can be effectively subjected to a kinetic racemate resolution by applying the Sharpless-Katsuki asymmetric epoxidation. The single-sided Wittig rearrangement of 2-allyloxy-2'-propyloxy-1,1'-binaphthyl proceeds without any diastereoselectivity as this substrate can only be monometalated and hence is incapable of intramolecular aggregate formation which is instrumental for the observed stereoselectivity.