Supplementary Material a,b,g -trifluoro alkanes: a stereoselective synthesis placing three vicinal fluorines along a hydrocarbon chain




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Supplementary Material




a,b,g-Trifluoro alkanes: A stereoselective synthesis placing three vicinal

fluorines along a hydrocarbon chain"




Marcello Nicoletti, David O’Hagan* and Alexandra M Z Slawin

a School of Chemistry, University of St Andrews, North Haugh, St Andrews, Fife, KY16 9ST, UK, Fax: 01334 463808; Tel: 01334 467176; E-mail: do1@st-andrews.ac.uk



RECEIVED DATE (will be automatically inserted after manuscript is accepted)


19F{1H}-NMR Spectra of compounds 1a – 2b (Data in Table in text)








S1



1.1 Experimental



All commercially available materials were purchased from Acros, Avocado, Fluka, Fluorochem or Sigma-Aldrich unless otherwise stated and purified according to literature procedures. The solvents used in reactions were dried, distilled and stored under nitrogen prior to use: Diethyl ether (sodium, benzofenone), dichloromethane (calcium hydride), tetrahydrofuran (sodium, benzophenone), pyridine and triethylamine (potassium hydroxide).

Air- and moisture sensitive reactions were carried out under a positive pressure of nitrogen/ argon in oven-dried (160C) glassware. Room temperature (RT) refers to 20-25C. Reaction temperatures of –78 [1]oC were obtained using solid CO2 pellets and acetone and temperatures of 0 oC were obtained in an ice/water bath. Reaction reflux condition were obtained using an oil bath equipped with a contact thermometer. Solvent evaporations were carried out under reduced pressure on a Büchi rotary evaporator.

Thin layer chromatography (TLC) was performed using Merck, Kieselgel 60 plates and were visualised by the use of a UV lamp or by the use of cerium (IV) sulfate stain. Liquid chromatograpy was performed using Merck, Kieselgel 60 (230-400) silica and preparative TLC was performed using Merck, Kieselgel 60 plates (1000 mm thickness).

Gas chromatography/mass spectroscopy (GC/MS) analysis of synthetic samples was conducted using an Agilent 5890 plus gas chromatograph equipped with a 5973N mass selective detector (EI mode) and 7683 series injector/autosampler, . Chromatographic separations were performed using a HP-5MS 5% Phenyl methyl siloxane capillary column (30 m x 250 mm with a film thickness of 0.25 mm). Chiral analysis were performed using a supelco 24304 Beta Dex 120 fused silica (30 m x 250 mm with a film thickness of 0.30 mm). The carrier gas was helium, with a flow rate of 1.1 ml min.-1 the injection volume was 1ml and the injection port temperature was 250 oC. Melting points were measured on a Gallenkamp Griffin MPA350BM2.5, melting point apparatus and are not corrected. Optical rotations were determined with a A-1000 polarimeter (optical polarimeter Ltd.) using a 2 dm cell, specific rotations are given in units of 10-1 deg.g-1 cm2. High-resolution CI and EI mass spectra were performed on a VG AUTOSPEC spectrometer. Carbon, hydrogen and nitrogen analyses were obtained using a CE Instrument EA 1110 CHNS analyser. Infrared spectra were recorded with Perkin Elmer 2000 FT-IR instrument as a thin layer between NaCl disks. Solid materials were prepared with KBr pellets. Values were rounded to 5 cm-1 upon manual assignment.

Nuclear magnetic resonance (NMR) spectra were measured for CDCl3 solutions on a Bruker Av-300.06 (7.0T) operating at 299.98 MHz for 1H, 75.45 MHz for 13C and 282.4 for 19F, and Varian Unity Plus 300 MHz operating at 299.98 MHz for 1H, 75.43 MHz. The assignments of the signals in the 1H NMR spectra are based on the first-order analysis of the spin systems and when required were confirmed by 1H{1H} decoupling and two-dimensional (2-D) (1H, 1H) homonuclear chemical shift correlation (COSY) experiments. 1H-NMR NOE experiments was conducted in a Varian Unity Plus 500 MHz (1H at 500.08 MHz) spectrometer. All chemical shifts are reported in parts per million (ppm) and quoted relative to the residual proton and/or fluorine peak CDCl3 (H 7.24 or C 77.0 ppm, for 1H and 13C, respectively), CFCl3 (0.0 ppm) for 19F. Proton-proton coupling constants (J) are given in Hertz. Spectral coupling patterns are designated as follows: s: singlet, d: doublet, t: triplet, q: quartet, m: multiplet, br: broad.
Preparation of (E)-non-3-en-2-ol (3a)

Sodium borohydride (2.7 g, 71.4 mmol) was added to a solution of trans-2-nonen-1-one (10 g, 71.4 mmol) and cerium (III) chloride heptahydrate (27 g, 71.4 mmol) in methanol (100 cm3) at 0 oC. The resulting suspension was stirred for 15 min. The reaction was concentrated by rotary evaporation and diluted with water (100 cm3) and a 1 N HCl solution (30 cm3). The aqueous phase was extracted into ether (3 x 100 cm3 ) and the combined organics were washed with brine (100 cm3), dried over magnesium sulfate, filtered and concentrated to yield 3a (9.0 g, 89%) as clear oil. This material was used without further purification. IR (neat), u : 3360, 2960, 2930, 2855, 1465, 1370, 1060, 965. 1H NMR (300 MHz, CDCl3), d : 0.87 (t, 3H, J= 6.6, CH3CH2), 1.21 (d, 3H, J= 6.4, CHOHCH3), 1.24-1.41 (m, 6H), 1.98 (q, 2H, J= 6.6, CH2CH=CH), 4.23 (p, 1H, J= 6.4, CHOHCH3), 5.42-5.66 (m, 2H, CH=CH). 13C NMR (75 MHz, CDCl3), d: 13.9 (s, CH3CH2), 22.4 (s, CH3CH2), 23.3 (s, CHOHCH3), 28.8 (s, CH3CH2CH2), 31.3 (s, CH2CH2CH=CH), 32.0 (s, CH2CH2CH=CH), 68.9 (s, CHOH), 131.1 (s, CH=CHCHOH), 134.0 (s, CH=CHCHOH). MS m/z (rel. int. %), (EI): 142 (15) [M+], 124 (20) [M-H2O], 109 (25) [M- H2O-Me].
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