An iridium-catalyzed intramolecular asymmetric allylic etherification of pyrimidinemethanols is described. In the presence of chiral-bridged biphenyl phosphoramidite ligand L3 and triethylborane, this process provided a class of novel pyrimidine-fused oxazepanes in up to 99% yield with 99.5% enantiomeric excess. The work addresses the challenge of insufficient nucleophilicity of aliphatic alcohols for allyl substitution and indicates the vital value of chiral-bridged biphenyl phosphoramidites. Various multifunctionalized transformations of the products further demonstrate the robust synthetic utility of this methodology.