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Chemo‐ and Enantioselective Intramolecular Silver‐Catalyzed Aziridinations
Author(s) -
Ju Minsoo,
Weatherly Cale D.,
Guzei Ilia A.,
Schomaker Jennifer M.
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201704786
Subject(s) - enantioselective synthesis , chemistry , chemoselectivity , nitrene , intramolecular force , nucleophile , kinetic resolution , catalysis , amine gas treating , combinatorial chemistry , substrate (aquarium) , ligand (biochemistry) , yield (engineering) , amination , aziridine , ring (chemistry) , organic chemistry , biochemistry , oceanography , receptor , materials science , geology , metallurgy
Asymmetric nitrene‐transfer reactions are a powerful tool for the preparation of enantioenriched amine building blocks. Reported herein are chemo‐ and enantioselective silver‐catalyzed aminations which transform di‐ and trisubstituted homoallylic carbamates into [4.1.0]‐carbamate‐tethered aziridines in good yields and with ee values of up to 92 %. The effects of the substrate, silver counteranion, ligand, solvent, and temperature on both the chemoselectivity and ee value were explored. Stereochemical models were proposed to rationalize the observed absolute stereochemistry of the aziridines, which undergo nucleophilic ring opening to yield enantioenriched amines with no erosion in stereochemical integrity.