PDF《- Supporting Information -》

-

1 - Isolation of the key intermediates in the catalyst free conversion of oxiranes to thiiranes in water at ambient temperature - Supporting Information - Christian M.

Kleiner, a Luise Horst, a Christian Würtele, b Rafael Wende, a and Peter R. Schreiner * a a Institut für Organische Chemie, Justus-Liebig-Universit?t Giessen, Heinrich-Buff-Ring 58, D-35392 Giessen, Germany;

prs@org.chemie.uni-giessen.de b Institut für Anorganische und Analytische Chemie, Justus-Liebig-Universit?t Giessen, Heirich-Buff-Ring 58, D-

35392 Giessen, Germany 1. General Methods and Procedures: Analytical Methods: All compounds were characterized by

1 H-NMR,

13 C-NMR, (

19 F-NMR), IR, MS and CHN analysis for new compounds. NMR spectra were recorded using Bruker Avance II

200 Microbay , Bruker Avance II

400 WB or Bruker Avance

600 MHz spectrometer at ambient temperature. All

1 H-NMR shifts were reported in parts per million (ppm) relative to the residual solvent peak (7.24 ppm for CDCl3, 2.05 ppm for d6-acetone). Proton- decoupled

13 C-NMR chemical shifts were reported relative to the solvent peak (77.1 ppm for CDCl3, 29.84 ppm for d6-acetone). Multiplicities are indicated as bs (broadened singlet), s (singlet), d (doublet), dd (doublet of doublet), t (triplet), q (quartet), quint (quintet), m (multiplet). Coupling constants (J) are in Hertz (Hz). Infrared spectra were recorded on a Bruker IFS

25 and IFS

48 spectrophotometer using KBr pallets, as thin film or by applying ATR technique. Absorptions were reported in reciprocal centimetres and indicated as vs (very strong), s (strong), m (middle) and w (weak), br (broad). Both conventional (LRMS) and high resolution mass spectra (HRMS) were conducted on a Finnigan MAT

95 instrument, ionization by electron impact at

70 eV. Melting points were measured with Electrothermal ? melting point apparatus IA6304 and are uncorrected. Optical rotations were measured with a Jasco P-2000 Polarimeter. Reactions were monitored by GC/MS (Hewlett Packard

5890 Series II Gas Chromatograph with Hewlett Packard

5971 A Mass Selective Detector) or TLC (silica gel coated plastic sheets, Machery-Nagel, Polygram ? SIL/UV254, 40x80 mm). Thin layer plates were visualized by irradiation with UV light at

254 nm and by staining the plates with alkaline KMnO4 solution followed by gentle heating. Isolation of the products was performed by flash chromatography using Merck silica gel (60, particle size 0.040 C 0.063 mm). Solvents for flash chromatography have been distilled once with a rotary evaporator prior to use. Chemical yields refer to pure isolated substances. Compound names are in agreement with the Beilstein nomenclature. Compound rac-1e was prepared according to the protocol of Barkworth et al.

1 Compound rac-1f was prepared according to the protocol of Alexakis et al.2 General Procedure: All reactions were carried out in a carrousel reaction station or in

5 mL cylindrical reaction vessels. Reaction mixtures were stirred magnetically with Teflon coated stirring bars. Epoxides were purchased in highest quality available. Liquid epoxides were distilled once through a

10 cm Vigreux-column and stored under argon in a fridge prior to use. Solid epoxides were used as received. Distilled water was used as received. Ammonium thiocyanate was purchased from Riedel-de Ha?n in puriss. quality and used as received. Solvents for column chromatography were distilled once and used without further purification.

2 mL of a stock solution of ammonium thiocyanate (c = 1M) were placed in the reaction vessel, and