Direct Nucleophilic Substitution of Alcohols Using an Immobilized Oxovanadium Catalyst

Abstract Direct nucleophilic substitution of alcohols with thiols or carbon nucleophiles was achieved using a mesoporous silica‐supported oxovanadium catalyst (VMPS4). Benzyl and allyl alcohols were compatible in this reaction under mild conditions, affording the products in high yields. The VMPS4 catalyst showed excellent chemoselectivity toward alcohols in the presence of acid‐labile functional groups, which is in contrast to that observed for the commonly used Lewis acid catalysts, which exhibit poor selectivity. The VMPS4 catalyst could be recycled by simple centrifugation, and the catalytic activity was maintained over seven cycles.