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Chemo- and Enantioselective Intramolecular Silver-Catalyzed Aziridinations.

ABSTRACT: 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.

SUBMITTER: Ju M

PROVIDER: S-EPMC5693370 | biostudies-literature | 2017 Aug

REPOSITORIES: biostudies-literature

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Chemo- and Enantioselective Intramolecular Silver-Catalyzed Aziridinations.

Ju Minsoo M Weatherly Cale D CD Guzei Ilia A IA Schomaker Jennifer M JM

Angewandte Chemie (International ed. in English) 20170712 33

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. Stereoche ...[more]

PMID: 28614622

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