Preparation of Fluorinated Tetrahydropyrans and Piperidines using a New Nucleophilic Fluorination Reagent DMPU/HF
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1 Supporting information Preparation of Fluorinated Tetrahydropyrans and Piperidines using a New Nucleophilic Fluorination Reagent DMPU/HF Otome E. Okoromoba, a Gerald B. Hammond, a, * Bo Xu b, * a Department of Chemistry, University of Louisville, Louisville, Kentucky 40292, United States; b College of Chemistry, Chemical Engineering and Biotechnology, Donghua University, 2999 North Renmin Lu, Shanghai , China Table of Contents 1. General Information... S2 2. General method for the oxa-prins fluorocyclization reaction... S2 3. General method for the aza-prins fluorocyclization reaction... S3 4. Spectroscopic data for compounds 3 and S3 5. Copies of NMR spectrums for compounds 3 and S9 6. References... S52 S1
2 1. General Information NMR spectra were recorded on a 400 MHz or a, 500 MHz spectrometers. Chemical shifts are given in ppm. The spectra are calibrated to the residual 1 H and 13 C and 19 F signals of the solvents. Multiplicities are abbreviated as follows: singlet (s), doublet (d), triplet (t), quartet (q), doubletdoublet (dd), quintet (quint), septet (sept), multiplet (m), and broad (br). Unless otherwise stated, starting materials were purchased from Aldrich and/or Fluka. Solvents were used as purchased. Conversion was monitored by thin layer chromatography (TLC) using Merck TLC silica gel 60 F254. Compounds were visualized by UV-light at 254 nm and by dipping the plates in an polymoybdenic acid (PMA), p-anisaldehyde, solutions or an aqueous potassium permanganate solution followed by heating depending on the compounds formed. DMPU/HF reagent was prepared according to a procedure previously reported by us. [Otome. E. Okoromoba, J. Han, G. B. Hammond, B. Xu. J. Am. Chem. Soc., 2014, 136 (41), ] 2. General method for the oxa-prins fluorocyclization reaction In a polyethylene vial charged with a magnetic stirring bar, homoallylic alcohol 1 (0.2 mmol) and aldehyde 2 (0.2 mmol) were dissolved in 0.5 ml dichloromethane, then HF-DMPU (HF content 65 % wt/wt, 58 µl, 2.1 mmol) was added to the mixture and was stirred for 3 h at room temperature. The progress of reaction can be monitored by TLC (green or dark brown dots on anisaldehyde stain). After completion of the reaction the mixture was quenched with cold water, and the organic phase was extracted with chloroform (5 ml). The organic phase was washed with aqueous sodium bicarbonate, a 2 M solution of sodium bisulfite and brine. Finally the organic phase was dried over sodium sulfate and was concentrated to dryness in vacuum. The crude product was chromatographed with a 10:1 mixture of hexanes and EtOAc to afford the corresponding fluoro-tetrahydropyrans 3. S2
3 3. General method for the aza-prins fluorocyclization reaction In a polyethylene vial charged with a magnetic stirrer, homoallylic tosylamine (0.2 mmol) and aldehyde 2 (0.2 mmol) were dissolved in 0.5 ml dichloroethane, then HF-DMPU (HF content 65 % wt/wt, 58 µl, 2.1 mmol) was added to the mixture and was stirred for 3 h at 55 o C. The progress of reaction can be monitored by TLC (green or dark brown dots on anisaldehyde stain). After completion of the reaction the mixture was quenched with cold water, and the organic phase was extracted with chloroform (2 ml). The organic phase was washed with aqueous sodium bicarbonate, a 2M solution of sodium bisulfite and brine. Finally the organic phase was dried over sodium sulfate and was concentrated to dryness in vacuum. The crude product was chromatographed with a 10:1 mixture of hexanes and EtOAc to afford the corresponding fluoropiperidine 5. Note: The aza-fluoro Prins products 5c-5e are contaminated with the corresponding starting material N-tosyl alkene (4), which are quite difficult to separate. This is due to the incomplete conversion of the aza-prins reaction involving the said aromatic aldehydes. A representative example of the spectra for compound 5e is given in S Spectroscopic data for compounds 3 and 5. 4-fluoro-2-phenyltetrahydro-2H-pyran (3a) Colorless oil, (24.7 mg) 1 H NMR (400 MHz, CDCl3): δ (m, 5 H), (m, JH,F = 49.1 Hz, 1 H), (m, 1 H), (m, 1 H), (m, 1 H), (m, 1 H), (m, 1 H), (m, 2H). Its spectroscopic data is consistent with literature report. 1 4-fluoro-2-(naphthalen-1-yl)tetrahydro-2H-pyran(3b) S3
4 Brown solid, (34 mg). 1 H NMR (400 MHz, CDCl3) δ (m, 4H), (m, 3H), (dtt, J= 49.0 Hz, 10.7 Hz, 5.1 Hz. 1H), 4.50 (d, J = 11.3 Hz, 1H), 4.27 (dd, J = 11.6, 5.6 Hz, 1H), 3.63 (t, J = 12.3 Hz, 1H), (m, 1H), (m, 1H), (m, 2H). 13 C NMR (100 MHz, CDCl3) δ , , , , , , , , , , , (d, J = Hz), (d, J = 11.4 Hz), (d, J = 11.9 Hz), (d, J = 17.1 Hz), (d, J = 17.7 Hz). 19 F NMR (376 MHz, CDCl3) δ (d, J = 49.0 Hz, 1F). MS: m/z= ([M] + ). ESI HRMS: calcd. for C15H15FONa + ([M+Na] + ) ; found (4-chlorophenyl)-4-fluorotetrahydro-2H-pyran (3c) Semisolid, (36.4 mg). 1 H NMR (CDCl3, 400 MHz): δ (4 H, m) (1 H, m), 4.30 (1 H, dd, J = 11.6, 2.0 Hz), (1 H, m), 3.56 (1 H, tt, J = 12.4, 1.6 Hz), (1 H, m), (1 H, m), 1.85 (1 H, dp, J = 11.2, 4.8 Hz), 1.71 (1 H, p, J = 10.0 Hz). Its spectroscopic data is consistent with literature report. 1a 2-(4-bromophenyl)-4-fluorotetrahydro-2H-pyran (3d) Brown solid, (46.4 mg) Cis isomer: 19 F NMR (CDCl3, 376 MHz): δ (m); trans isomer: 19 F NMR (CDCl3, 376 MHz) δ (m). Its spectroscopic data is consistent with literature report. 2 4-fluoro-2-(4-nitrophenyl)tetrahydro-2H-pyran (3e) S4
5 Solid (36.1mg) Cis isomer: 19 F NMR (CDCl3, 376 MHz): δ (m); trans isomer 19 F NMR (CDCl3, 376 MHz) δ (m). Its spectroscopic data is consistent with literature report. 2 4-fluoro-2-(4-(trifluoromethyl)phenyl)tetrahydro-2H-pyran (3f) Yellow solid, (45.3 mg). This compound is known: 1 H NMR (CDCl3, 400 MHz): δ 7.61 (2 H, d, J = 8.0 Hz), 7.46 (2 H, d, J = 8.0 Hz), 7.46 (2 H, d, J = 8.0 Hz), (1 H, m), 4.37 (1 H, dd, J = 11.2, 2.0 Hz), (1 H, m), 3.57 (1 H, tt, J = 14.0, 2.0 Hz), (1 H, m), (1 H, m), (1 H, m), d (m, 1 H). Its spectroscopic data is consistent with literature report. 1a 4-fluoro-2-(4-isopropylphenyl)tetrahydro-2H-pyran (3g) Yellow solid, (33.9 mg): 1 H NMR (400 MHz, CDCl3) δ (m, 5H), (m, 1H), (m, 1H), 4.20 (dt, J = 11.6, 5.7 Hz, 1H), 3.56 (td, J = 12.4, 1.5 Hz, 1H), (m, 1H), (m, 1H), (m, 1H), (m, 2H), 1.25 (dd, J = 6.9, 1.5 Hz, 6H). 13 C NMR (100 MHz, CDCl3) δ , , , , , , (d, J = Hz), (d, J = 11.4 Hz), (d, J = 11.9 Hz), (d, J = 16.9 Hz), (s, 4H), (s, 13 H), (d, J = 17.5 Hz), F NMR (376 MHz, CDCl3) δ (dd, J = 49.2, 4.5 Hz, 1F). MS: m/z [M] +. ESI HRMS: calcd. for C14H20FO + ([M+H] + ) ; found fluoro-2-(p-tolyl)tetrahydro-2H-pyran (3h) S5
6 Colorless oil, (28 mg). 1 H NMR (400 MHz, CDCl3): δ = 7.22 (d, J = 8.1 Hz, 2 H), 7.14 (d, J = 8.1 Hz, 2 H), (m, JH,F = 49.1 Hz, 1 H), (m, 2H), (m, 1 H), 2.32 (s, 3 H), (m, 1 H), (m, 1 H), (m, 2 H). Its spectroscopic data is consistent with literature report. 1b 4-fluoro-2-(2-nitrophenyl)tetrahydro-2H-pyran (3i) Yellow oil, (33.6 mg). 1 H NMR (CDCl3, 400 MHz): d (1 H, m), (1 H, m), (1 H, m), (1 H, m), 3.58 (1 H, tt, J = 12.4, 1.6 Hz), (1 H, m), 4.70 (1 H, dd, J = 11.2, 2.0 Hz), (1 H, m), 4.90 (1 H, dd, J = 12.8, 1.6 Hz), (1 H, m), (1 H, m), 7.81 (1 H, d, J = 8.0 Hz), 7.94 (1 H, d, J = 8.0 Hz). Its spectroscopic data is consistent with literature report. 1a 3-bromo-2-(4-fluorotetrahydro-2H-pyran-2-yl)-6-methoxyphenol (3k) dark brown solid (33.7 mg): 1 H NMR (400 MHz, CDCl3) δ 7.01 (d, J = 8.7 Hz, 1H), 6.68 (d, J = 8.7 Hz, 1H), 4.94 (d, J = 11.8 Hz, 1H), (m, 1H), (m, 1H), 3.85 (s, 3H), 3.62 (t, J = 12.5 Hz, 1H), (m, 1H), (m, 1H), (m, 2H). 13 C NMR (100 MHz, CDCl3) δ , , , , , (d, J = Hz), (d, J = 12.4 Hz), (d, J = 12.1 Hz), 56.16, (d, J = 18.1 Hz), (d, J = 18.6 Hz). 19 F NMR (376 MHz, CDCl3) δ (d, J = 46.8 Hz, 1F). MS: m/z = [M] +. ESI HRMS: calcd. for C12H15FO3Na ; found , cald. For C12H16FO3 + ([M+H] + ) ; found cyclohexyl-4-fluorotetrahydro-2H-pyran (3l) S6
7 Light yellow Oil, (33 mg). Cis isomer: 19 F (CDCl3, 376 MHz): δ (m); trans isomer: 19 F NMR (CDCl3, 376 MHz) δ (m). Its spectroscopic data is consistent with literature report. 3 2-cyclohexyl-4-fluoro-1-tosylpiperidine (5a) Color less oil, (63.4 mg). Cis isomer: 19 F NMR (CDCl3, 376 MHz): δ (m); trans isomer: 19 F NMR (CDCl3, 376 MHz) δ (m). Its spectroscopic data is consistent with literature report. 1b 4-fluoro-2-pentyl-1-tosylpiperidine (5b) Colorless oil, (60.2 mg) Cis isomer: 19 F NMR (CDCl3, 376 MHz): δ (m); trans isomer: 19 F NMR (CDCl3, 376 MHz) δ -179 (m). Its spectroscopic data is consistent with literature report. 2 4-fluoro-2-phenyl-1-tosylpiperidine (5c) Colorless oil, (27 mg). Cis isomer: 19 F NMR (CDCl3, 376 MHz): δ (m); trans isomer: 19 F NMR (CDCl3, 376 MHz) δ (m). Its spectroscopic data is consistent with literature report. 1b 2-(4-bromophenyl)-4-fluoro-1-tosylpiperidine (5d) S7
8 White solid, (40 mg) Cis isomer: 19 F NMR (CDCl3, 376 MHz): δ (m); trans isomer: 19 F NMR (CDCl3, 376 MHz) δ (m). Its spectroscopic data is consistent with literature report. 2 4-fluoro-2-(4-nitrophenyl)-1-tosylpiperidine (5e) White solid, (23.1 mg). Cis isomer: 19 F NMR (CDCl3, 376 MHz): δ (m); trans isomer: 19 F NMR (CDCl3, 376 MHz) δ (m). Its spectroscopic data is consistent with literature report. 2 S8
9 5. Copies of NMR spectrums for compounds 3 and 5. 1 H NMR Spectrum 3a S9
10 13 C NMR Spectrum 3a S10
11 19 F NMR Spectrum 3a S11
12 1 H NMR Spectrum 3b S12
13 13 C NMR Spectrum 3b S13
14 19 F NMR Spectrum 3b S14
15 1 H NMR Spectrum 3c S15
16 13 C NMR Spectrum 3c S16
17 19 F NMR Spectrum 3c S17
18 1 H NMR Spectrum 3d S18
19 13 C NMR Spectrum 3d S19
20 19 F NMR Spectrum 3d S20
21 1 H NMR Spectrum 3e S21
22 13 C NMR Spectrum 3e S22
23 19 F NMR Spectrum 3e S23
24 1 H NMR Spectrum 3f S24
25 13 C NMR Spectrum 3f S25
26 19 F NMR Spectrum 3f S26
27 1 H NMR Spectrum 3g S27
28 13 C NMR Spectrum 3g S28
29 19 F NMR Spectrum 3g S29
30 1 H NMR Spectrum 3h S30
31 13 C NMR Spectrum 3h S31
32 19 F NMR Spectrum 3h S32
33 1 H NMR Spectrum 3i S33
34 13 C NMR Spectrum 3i S34
35 19 F NMR Spectrum 3i S35
36 1 H NMR Spectrum 3k S36
37 13 C NMR Spectrum 3k S37
38 19 F NMR Spectrum 3k S38
39 1 H NMR Spectrum 3l S39
40 13 C NMR Spectrum 3l S40
41 19 F NMR Spectrum 3l S41
42 1 H NMR Spectrum 5a S42
43 13 C NMR Spectrum 5a S43
44 19 F NMR Spectrum 5a S44
45 1 H NMR Spectrum 5b S45
46 13 C NMR Spectrum 5b S46
47 19 F NMR Spectrum 5b S47
48 1 H NMR Spectrum 5e: Representative spectra for aromatic aza-prins S48
49 19 F NMR Spectrum 5e: Representative spectra for aromatic aza-prins S49
50 HRMS copies of unknown compounds OE_1_Inaphtyl_pos #31-74 RT: AV: 44 NL: 2.80E3 T: FTMS + p ESI Full ms [ ] Relative Abundance m/z OE_1_Isoprop_pos #15-29 RT: AV: 15 NL: 1.34E5 T: FTMS + p ESI Full ms [ ] C 14 H 20 O1 F H + 60 Relative Abundance C 8 H 19 O2 N 4 F C2 O7 N4 P C13 H23 O C 14 H 14 O m/z S50
51 OE_1_Br_pos #28-40 RT: AV: 13 NL: 2.69E6 T: FTMS + p ESI Full ms [ ] Na Relative Abundance m/z OE_1_Br_pos #28-40 RT: AV: 13 NL: 5.97E5 T: FTMS + p ESI Full ms [ ] Relative Abundance H m/z S51
52 6. References 1. (a) Bondalapati, S.; Reddy, U. C.; Kundu, D. S.; Saikia, A. K. J. Fluorine Chem. 2010, 131, ; (b) Kishi, Y.; Inagi, S.; Fuchigami, T. Eur. J. Org. Chem. 2009, 2009, Launay, G. G.; Slawin, A. M. Z.; O'Hagan, D. Beilstein J. Org. Chem. 2010, 6, DOI: /bjoc Kishi, Y.; Nagura, H.; Inagi, S.; Fuchigami, T. Chem. Commun. 2008, S52
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