Catalytic stereoselective alkene aziridination with sulfonimidamides

Diastereoselective copper-catalyzed alkene aziridination has been investigated using chiral nitrenes generated from sulfonimidamides in the presence of an iodine(III) oxidant. Starting from a stoichiometric amount of the substrates, the corresponding aziridines were isolated with excellent yields of up to 96%. Good levels of asymmetric induction were obtained in the case of electron-poor olefins, with an optimal de of 94% being reached starting from tert-butyl acrylate. Matching and mismatching effects were also observed upon the use of chiral copper catalysts for the aziridination of styrene.

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(S)-N-(p-Toluenesulfonyl)-p-toluenesulfonimidamideC14H16N2O3S2Ee = 99%[α]D20=-110 (c 0.47, acetone)Source of chirality: resolution with (R)-1-phenylethylamineAbsolute configuration: (S)

(R)-N-(p-Toluenesulfonyl)-p-toluenesulfonimidamideC14H16N2O3S2Ee = 99%[α]D20=+110 (c 0.47, acetone)Source of chirality: resolution with (S)-1-phenylethylamineAbsolute configuration: (R)

(S)-N-(p-Toluenesulfonyl)-p-nitrobenzenesulfonimidamideC13H13N3O5S2Ee = 99%[α]D20=-140 (c 0.54, acetone)Source of chirality: resolution with (R)-1-phenylethylamineAbsolute configuration: (S)

(S)-N-(p-Toluenesulfonyl)-p-chlorobenzenesulfonimidamideC13H13ClN2O3S2Ee = 98%[α]D20=-132 (c 1.00, acetone)Source of chirality: resolution with (R)-1-phenylethylamineAbsolute configuration: (S)