Catalytic α‑Selective Deuteration of Styrene Derivatives

We report an operationally simple protocol for the catalytic α-deuteration of styrenes. This process proceeds via the base-catalyzed reversible addition of methanol to styrenes in DMSO<i>-d</i><sub>6</sub> solvent. The concentration of methanol is shown to be critical for high yields and selectivities over multiple competing side reactions. The synthetic utility of α-deuterated styrenes for accessing deuterium-labeled chiral benzylic stereocenters is demonstrated.