Intermolecular Catalytic Asymmetric Iodoetherification of Unfunctionalized Alkenes.

A newly prepared trinuclear Zn3-(R,S,S)-aminoiminobinaphthoxide complex (triZn-II) catalyzed the first general intermolecular asymmetric iodoetherification of unfunctionalized alkenes. Using triZn-II, the iodoetherification reaction of unfunctionalized alkenes with o-nitrophenols proceeded smoothly to give the products with up to 92.5:7.5 er, and diene substrates were converted to the products with up to 99:1 er with the formation of a meso-isomer (dl/meso = 78/22). The chiral iodoethers gave a new platform for the synthesis of chiral morpholines.

Catalytic Asymmetric Iodoesterification of Simple Alkenes.

Catalytic asymmetric iodoesterification of simple alkenes was achieved using a dinuclear zinc-3,3'-(R,S,S)-bis(aminoimino)binaphthoxide (di-Zn) complex. For iodoesterification using p-methoxybenzoic acid, the N-iodonaphthalenimide (NIN)-I2 system was effective for producing iodoesters in a highly enantioselective manner. The synthetic utility of chiral iodo-p-methoxybenzoates was also demonstrated. The quartet of metal ionic bond, hydrogen bond, halogen bond, and π-π stacking is harmonized on the single reaction sphere of di-Zn catalyst for enabling the highly enantioselective catalytic asymmetric iodoesterification of simple alkenes for the first time.