Stereoinversion of tertiary alcohols to tertiary-alkyl isonitriles

Shenvi et al. have reported a stereochemical inversion of tertiary alcohols to tertiary alkylisonitriles and amine. In this report, tertiary alkylisonitriles are given from the corresponding tertiary alcohols with inversion of chirality by the trifluoroacetylation of the starting alcohol’s subsequent Sc(OTf)₃ catalyzed reaction with an excess amount of TMSCN. This reaction is chemoselective for tertiary-alcohols in preference to primary or secondary ones, opposite to the S_N2 reaction, thereby complementing the selectivity of the Mitsunobu reaction.