A base-catalyzed approach for the anti-Markovnikov hydration of styrene derivatives

The base-catalyzed addition of 1-cyclopropylethanol to styrene derivatives with an acidic reaction workup enables anti-Markovnikov hydration. The use of either catalytic organic superbase or crown ether-ligated inorganic base permits hydration of a wide variety of styrene derivatives, including electron-deficient, ortho-substituted and heteroaryl variants. This protocol complements alternative routes to terminal alcohols that rely on stoichiometric reduction and oxidation processes. The utility of this method is demonstrated through multigram scale reactions and its use in a two-step hydration/cyclization process of ortho-halogenated styrenes to prepare 2,3-dihydrobenzofuran derivatives.