Hexane → 5-Fluoro-1-phenylhept-6-en-3-ol

HRID 2101654Notes

Reaction equation

HRID 2101654 reaction equation
[C:1]1([CH2:7][CH2:8][CH:9]([OH:18])[CH2:10][CH:11]=[CH:12][CH2:13][Si](C)(C)C)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.C(=O)(O)[O-].[Na+].[B-](F)(F)(F)[F:25].[B-](F)(F)(F)F.C1[N+]2(CCl)CC[N+](F)(CC2)C1.CCCCCC>C(#N)C.CCOCC>[F:25][CH:11]([CH:12]=[CH2:13])[CH2:10][CH:9]([OH:18])[CH2:8][CH2:7][C:1]1[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1

Participants

7

Reactant 4

HCID 8058HexaneHCID 516892Sodium BicarbonateHCID 2724933SelectfluorHCID 688552291-Phenyl-7-(trimethylsilyl)-hept-5-en-3-ol

Product 1

HCID 578018035-Fluoro-1-phenylhept-6-en-3-olYield 64%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 6342AcetonitrileSolvent

Procedure

A solution of 1-phenyl-7-trimethylsilanyl-hept-5-en-3-ol (776 mg, 2.96 mmol, 1 eq) in acetonitrile (30 mL), with sodium bicarbonate (497 mg, 5.92 mmol, 2 eq), was treated with Selectflour™ (2.097 g, 5.92 mmol, 2 eq) and stirred at room temperature under an atmosphere of argon for 18 h. The reaction was then concentrated under reduced pressure and water (10 mL) was added and then extracted with ether (3×15 mL). The combined organic phases were dried over MgSO4, filtered and the solvent removed under reduced pressure. Column chromatography (hexane:ether, 95:5, 9:1, 85:15) gave 5-fluoro-1-phenylhept-6-en-3-ol as a colourless oil (397 mg, 64% yield). For major diastereomer: 1H NMR (400 MHz, CDCl3) δ 1.63-2.04 (m, 4H, CH2CHF, CH2CHOH), 2.67-2.74 (m, 1H, PhCH2), 2.78-2.86 (m, 1H, PhCH2), 3.92-3.98 major (m, 1H, CHOH), 5.05-5.20 (m, 1H, CHF), 5.22-5.27 (m, 2H, CHCH2), 5.86-5.99 (m, 1H, CHCH2), 7.19-7.33 (m, 5H, Ph); 13C NMR (100 MHz, CDCl3) δ 31.8 (PhCH2), 39.1 (PhCH2CH2), 42.4 (CHOHCH2), 67.2 (CHOH), 90.0-91.7 (d, CHF, J=165 Hz), 116.7 (CHCH2), 125.9 (Ph), 128.4 (Ph), 136.0 (CHCH2), 141.7 (Ph); 19F NMR (376.5 MHz , CDCl3) δ −177. For minor diastereomer: 1H NMR (400 MHz, CDCl3) δ 1.63-2.04 (m, 4H, CH2CHF, CH2CHOH), 2.67-2.74 (m, 1H, PhCH2), 2.78-2.86 (m, 1H, PhCH2), 3.85-3.91 (m, 1H, CHOH), 5.05-5.20 (m, 1H, CHF), 5.22-5.27 (m, 2H, CHCH2), 5.33-5.39 (m, 1H, CHCH2), 7.19-7.33 (m, 5H, Ph); 13C NMR (100 MHz, CDCl3) δ 31.8 (PhCH2), 39.1 (PhCH2CH2), 42.4 (CHOHCH2), 68.9 (CHOH), 92.3-93.9 (d, CHF, J=164 Hz), 116.7(CHCH2), 125.9 (Ph), 128.4 (Ph), 136.0 (CHCH2), 141.7 (Ph); 19F NMR (376.5 MHz, CDCl3) δ −180. IR (v, cm−1) 3418 (OH), 1651 (C═C), 1496 (Ar), 1455 (Ar); MS (GCT, CI+) m/z 226.2 [M+NH4]+ HRMS required for C13H21FON: 226.1607, found 226.1611.

Workup

  1. concentrationThe reaction was then concentrated under reduced pressure and water (10 mL)
  2. additionwas added
  3. extractionextracted with ether (3×15 mL)
  4. dry with materialThe combined organic phases were dried over MgSO4
  5. filtrationfiltered
  6. customthe solvent removed under reduced pressure

Sources & evidence

ORD record
ord-28cb7f25a446456081deca36adae846b
Source dataset
uspto-grants-2009_08
Patent number
US07572928B2

Reaction notes

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