Asymmetric Synthesis of Tertiary Alcohols and Thiols via Nonstabilized Tertiary α-Oxy- and α-Thio-Substituted Organolithium Species

Nonstabilized α‐O‐substituted tertiary organolithium species are difficult to generate, and the α‐S‐substituted analogues are configurationally unstable. We now report that they can both be generated easily and trapped with a range of electrophiles with high enantioselectivity, providing ready access to a range of enantioenriched tertiary alcohols and thiols. The configurational stability of the α‐S‐organolithium species was enhanced by using a less coordinating solvent and short reaction times

Stereospecific conversion of alcohols into pinacol boronic esters using lithiation–borylation methodology with pinacolborane

The synthesis of primary and secondary pinacol boronic esters via lithiation–borylation of carbamates and benzoates with pinacolborane is described. This new protocol enables the highly selective synthesis of enantioenriched and geometrically defined boronic esters that cannot otherwise be accessed by alternative methodologies