Diethyl Ether → {[3-Fluoro-5-(2-phenylethyl)tetrahydrofuran-2-yl]methyl}(triisopropyl)silane

HRID 2101656Notes

Reaction equation

HRID 2101656 reaction equation
[C:1]1([CH2:7][CH2:8][CH:9]([OH:24])[CH2:10][CH:11]=[CH:12][CH2:13][Si:14]([CH:21]([CH3:23])[CH3:22])([CH:18]([CH3:20])[CH3:19])[CH:15]([CH3:17])[CH3:16])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[B-](F)(F)(F)[F:26].[B-](F)(F)(F)F.C1[N+]2(CCl)CC[N+](F)(CC2)C1.CCCCCC.CCOCC>C(#N)C>[F:26][CH:11]1[CH2:10][CH:9]([CH2:8][CH2:7][C:1]2[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=2)[O:24][CH:12]1[CH2:13][Si:14]([CH:21]([CH3:23])[CH3:22])([CH:15]([CH3:16])[CH3:17])[CH:18]([CH3:20])[CH3:19]

Participants

6

Reactant 4

HCID 3283Diethyl EtherHCID 8058HexaneHCID 2724933SelectfluorHCID 688557041-Phenyl-7-(triisopropylsilyl)hept-5-en-3-ol

Product 1

HCID 68854874{[3-Fluoro-5-(2-phenylethyl)tetrahydrofuran-2-yl]methyl}(triisopropyl)silaneYield 100.1%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

A solution of 1-phenyl-7-(triisopropylsilyl)hept-5-en-3-ol (149 mg, 0.43 mmol, 1 eq) in acetonitrile (5 mL) was treated with Selectfluor (152 mg, 0.43 mmol, 1 eq) and stirred at room temperature under an atmosphere of argon for 18 h. The acetonitrile was removed under reduced pressure and the reaction was quenched with saturated aqueous sodium hydrogen carbonate (5 mL). It was then extracted with ether (3×10 mL), dried over MgSO4, filtered and the solvent removed under reduced pressure to give a pale yellow oil. Column chromatography (hexane:ether, 9:1) gave {[3-fluoro-5-(2-phenylethyl)tetrahydrofuran-2-yl]methyl}(triisopropyl)silane as a colourless oil (157 mg, 66% yield). For the major diastereomer depicted on the left hand side in the pair of formulae above: 1H NMR (400 MHz, CDCl3) δ 0.92-1.00 (dd, 1H, CH2Si, J=14.4, 5.6 Hz), 1.08-1.10 (m, 21H, SiCHCH3), 1.19-1.26 (m, 1H, CH2Si) 1.66-1.89 (m, 2H, PhCH2CH2), 1.93-2.02 (m, 1H, CH2CHF), 2.26-2.43 (m, 1H, CH2CHF), 2.60-2.83 (m, 2H, PhCH2), 3.70-3.81 (m, 1H, PhCH2CH2CHO), 4.06-4.17 (dddd, 1H, OCHCHF, J=27.6, 8.4, 5.6, 2.8 Hz), 4.83-4.98 (m, 1H, CHF); 13C NMR (100 MHz, CDCl3) δ 8.21-8.26 (CH2Si), 11.4 (Si(CH(CH3)2)3), 18.9 (Si(CH(CH3)2)3), 32.5 (PhCH2), 38.0 (PhCH2CH2), 39.2-39.4 (d, CH2CHF, J=21 Hz), 76.1 (PhCH2CH2CHO), 78.6-78.8 (d, CHFCHO, J=20 Hz), 94.6-96.5 (d, CHF, J=182), 125.7 (Ph), 125.8 (Ph), 128.3 (Ph), 128.4 (Ph), 142.1 (Ph); 19F NMR (376.5 MHz, CDCl3) δ −191.5 For the major diastereomer depicted on the right hand side in the pair of formulae above: 1H NMR (400 MHz, CDCl3) δ 0.92-1.00 (dd, 1H, CH2Si, J=14.4, 5.6 Hz), 1.08-1.10 (m, 21H, SiCHCH3 ), 1.19-1.26 (m, 1H, CH2Si) 1.66-1.89 (m, 2H, PhCH2CH2), 1.93-2.02 (m, 1H, CH2CHF), 2.26-2.43 (m, 1H, CH2CHF), 2.60-2.83 (m, 2H, PhCH2), 3.70-3.81 (m, 1H, PhCH2CH2CHO), 4.20-4.27 (m, 1H, OCHCHF), 4.78-4.93 (m, 1H, CHF); 13C NMR (100 MHz, CDCl3) δ 8.75-8.82 (CH2Si), 11.4 (Si(CH(CH3)2)3), 18.9 (Si(CH(CH3)2)3), 32.7 (PhCH2), 38.2 (PhCH2CH2), 39.6-39.9 (d, CH2CHF, J=21 Hz), 77.2 (PhCH2CH2CHO), 80.1-80.3 (d, CHFCHO, J=21 Hz), 94.0-94.5 (d, CHF, J=183), 125.8 (Ph), 128.3 (Ph), 128.4 (Ph), 128.5 (Ph), 142.1 (Ph); 19F NMR (376.5 MHz, CDCl3) δ −185.5; IR (v, cm−1) 3027 (Ar—H), 1496 (Ar), 1464 (Ar), 1384 (Ar), 1096 (C—O—C), 699 (Si—C); MS (GCT, CI+) m/z 226.2 [M+NH4]+ HRMS required for C22H41FNOSi: 382.2941, found 382.2935.

Workup

  1. customThe acetonitrile was removed under reduced pressure
  2. customthe reaction was quenched with saturated aqueous sodium hydrogen carbonate (5 mL)
  3. extractionIt was then extracted with ether (3×10 mL)
  4. dry with materialdried over MgSO4
  5. filtrationfiltered
  6. customthe solvent removed under reduced pressure
  7. customto give a pale yellow oil

Sources & evidence

ORD record
ord-d224825e026d417d99960fbb63f38cf4
Source dataset
uspto-grants-2009_08
Patent number
US07572928B2

Reaction notes

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