N-(2-(Trimethylsilyl)ethanesulfonyl)imino]phenyliodane

Abstract

[236122-13-7] C11H18INO2SSi (MW 383.32) InChI = 1S/C11H18INO2SSi/c1-17(2,3)10-9-16(14,15)13-12-11-7-5-4-6-8-11/h4-8H,9-10H2,1-3H3 InChIKey = PDQYQRCBDUNXBI-UHFFFAOYSA-N (iodine(III) reagent used as a nitrogen atom source in the transition-metal catalyzed aziridination of olefins or in the sulfoximination of sulfoxides)1, 2 Alternate Name: phenyl{[(2-(trimethylsilyl)ethyl)sulfonyl]amino}iodonium, inner salt. Physical Data: mp 84–85.5 °C.3 Solubility: slightly soluble in CH2Cl2, CHCl3 (slow decomposition observed). Form Supplied in: pale yellow solid. Typical impurities are SesNH2 and PhI. Analysis of Reagent Purity: 1H NMR analysis of iminoiodane purity is unreliable since it is unstable and only slightly soluble in CDCl3. Iodometric titration is possible. Another test of purity could be the use of the reagent in a standard aziridination applied to a five-molar excess of styrene.4 Preparative Methods: the protocol is adapted from the original synthesis of I-N ylides.5 SesNH2 (prepared by reaction of Ses-Cl6 with concentrated aqueous ammonia at 0 °C in CH3CN), KOH pellets (2.5 equiv), and PhI(OAc)2 (1.0 equiv) are successively added to anhydrous methanol at 0 °C. After 3 h of stirring from 0 °C to rt, an expeditive work-up, described below, is followed. The mixture is diluted at 0 °C with freshly distilled CH2Cl2 and washed with ice water. After separation, the organic phase is dried over MgSO4 and evaporated to dryness at room temperature. More reliable and practical now is the in situ generation of PhINSes from PhIO and SesNH2.7 This procedure is strongly recommended since the isolation of iminoiodinanes is particularly troublesome. Handling, Storage, and Precautions: for optimal results, the reagent should be stored under argon at −20 °C. Irritating to skin. As with any hypervalent iodine reagent, caution is required while heating.