The enantioselective formation of α-aryloxy-β-keto esters is described for the first time. Lewis acid catalyzed enantioselective chlorination of β-keto esters and subsequent SN 2 reactions with phenols yielded α-aryloxy-β-keto esters with up to 96% ee. Favorskii rearrangement of α-chloro-β-keto esters was also found to give 1,2-diesters with slightly reduced enantiopurity.

An asymmetric synthesis of various trifluoromethyl cyclopropanes from olefins, such as vinyl ferrocene, vinyl ethers, vinyl amines, vinyl carbamates and dienes, was achieved by using Ru(ii)-Pheox catalysts. This catalytic system can function at a low catalyst loading (3 mol%) compared with those reported previously, and the desired cyclopropane products are obtained in high yields with excellent diastereoselectivity (up to >99 : 1) and enantioselectivity (up to 97% ee).

A highly stereoselective cyclopropanation of various olefins with diazosulfones catalyzed by chiral Ru(ii)-Pheox complexes was developed to give chiral cyclopropyl sulfones in high yields (up to 99%) with excellent trans-selectivity and enantioselectivity (up to 98% ee).

For the first time, the enantioselective synthesis of α‐aryloxy‐β‐keto esters through the sequential enantioselective chlorination of cyclic and non‐cyclic β‐keto esters followed by nucleophilic substitution of chlorine atoms with phenols is described.