Enantioselective Construction of Pyrimidine‐Fused Diazepinone Derivatives Bearing a Tertiary Stereogenic Center Enabled by Iridium‐Catalysed Intramolecular Allylic Substitution.

The iridium‐catalysed enantioselective intramolecular allylic substitution of pyrimidine‐tethered allylic carbonates was developed. A wide range of chiral pyrimidine‐fused diazepinone derivatives were successfully constructed in 88–96% yields with 85–99% ees. This work further highlights the power of chiral‐bridged biphenyl phosphoramidites in asymmetric synthesis. [ABSTRACT FROM AUTHOR]