Diastereoselective rhodium-catalyzed nitrene transfer starting from chiral sulfonimidamide-derived iminoiodanes

The dirhodium-catalyzed aziridination of olefins with chiral sulfonimidamides as iminoiodane precursors has been investigated under stoichiometric conditions. Diastereoisomeric excesses of up to 82% have been achieved using [Rh2{(S)-nttl}4] as catalyst. Matching and mismatching effects were observed upon use of chiral rhodium(II) carboxylate catalysts.

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N-(p-Toluenesulfonyl)-p-toluenesulfonimidamideC14H16N2O3S2Ee = 95%[α]D23=+117 (c 0.5, acetone)Source of chirality: resolution with (S)-1-phenylethylamineAbsolute configuration: (R)

N-(p-Nitrobenzenesulfonyl)-p-toluenesulfonimidamideC13H13N3O5S2Ee = 90%[α]D23=-117 (c 0.5, acetone)Source of chirality: resolution with (S)-1-phenylethylamineAbsolute configuration: (S)