This paper describes an effective chiral base-catalyzed biomimetic transamination of α-keto esters using simple benzyl amines. A wide variety of α-amino esters containing various functional groups can be synthesized in high enantioselectivity and reasonable yield.

Despite their broad utility, the synthesis of ortho‐quinones remains a significant challenge, in particular, access to electron‐deficient derivatives remains an unsolved problem. Reported here is the first general method for the synthesis of electron‐deficient ortho‐quinones by direct oxidation of phenols. The reaction is enabled by a novel bidentate nitrogen‐ligated iodine(V) reagent, a previously unexplored class of compounds which we have termed Bi(N)‐HVIs. The reaction is extremely general and proceeds with excellent regioselectivity for the ortho over para isomer. Functionalization of the ortho‐quinone products was examined, resulting in a facile one‐pot synthesis of catechols, as well as the incorporation of a variety of heteroatom nucleophiles. This method represents the first synthetic application of Bi(N)‐HVIs and demonstrates their potential as a platform for the further development of highly reactive, but also highly tunable, I(V) reagents.

An efficient asymmetric biomimetic transamination of α-keto esters with quinine derivatives as chiral bases was described. A wide variety of α-amino esters containing various functional groups can be synthesized in high yield and enantioselectivity.