Direct Site‐Selective Deoxygenation of Benzylalcohol Derivatives

A simple yet efficient method is presented for direct and site‐selective deoxygenation of benzyl alcohol derivatives, including polyols, without requiring preactivation. This reaction system, consisting of Hantzsch ester, Cs 2 CO 3 , and a photocatalyst under photoirradiation, enables direct and site‐selective deoxygenation. Mechanistic studies reveal that in situ reversible acylative activation of hydroxy groups plays a pivotal role in achieving unique selectivity. This approach offers a general and practical strategy for the selective transformation of polyols.