An effective implementation of the Corey-Seebach dithiane addition for the synthesis of photolabile alkoxy benzoin adducts is reported. The method allows for the facile synthesis of photolabile 3′, 5′-dimethoxybenzoin protected compounds in near quantitative yield and is general in that it can be used for the synthesis of both symmetrical and unsymmetrical benzoins. Importantly, the dithiane intermediate reported is a versatile starting material for ...