Pyridine, hydrofluoride (1:1) → HCID 69216260, compound

HRID 2252476Notes

Reaction equation

HRID 2252476 reaction equation
C1C=CN=CC=1.F.[Si:8]([O:15][C@@H:16]([CH2:42][CH2:43][O:44][Si](C(C)(C)C)(C)C)[C@H:17]([CH3:41])/[CH:18]=[CH:19]/[CH2:20][O:21][C:22]([C:35]1[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=1)([C:29]1[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1)[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1)([C:11]([CH3:14])([CH3:13])[CH3:12])([CH3:10])[CH3:9]>N1C=CC=CC=1.C1COCC1>[Si:8]([O:15][C@H:16]([C@H:17]([CH3:41])/[CH:18]=[CH:19]/[CH2:20][O:21][C:22]([C:29]1[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1)([C:35]1[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=1)[C:23]1[CH:24]=[CH:25][CH:26]=[CH:27][CH:28]=1)[CH2:42][CH2:43][OH:44])([C:11]([CH3:14])([CH3:13])[CH3:12])([CH3:10])[CH3:9]

Participants

5

Reactant 2

HCID 64774Pyridine, hydrofluoride (1:1)HCID 11157936HCID 11157936, compound

Product 1

HCID 69216260HCID 69216260, compoundYield 89.2%

Reagents, catalysts & solvents 2

HCID 1049PyridineSolventHCID 8028TetrahydrofuranSolvent

Procedure

HF-pyridine in pyridine (40 mL, prepared by slow addition of 12 mL pyridine to 3 mL HF-pyridine complex followed by dilution with 25 mL THF) was added to a solution of TBS ether 12 (4.46 g, 7.07 mmol) in THF (10 mL). The mixture was stirred overnight at room temperature and quenched with sat'd NaHCO3 (100 mL). The aqueous layer was separated and extracted with Et2O (3×50 mL). The combined organic layers were washed with sat'd CUSO4 (3×50 mL), dried over MgSO4, and concentrated. Flash column chromatography (EtOAc/hexane 1:4) afforded 3.26 g (89%) of alcohol 13 as a colorless oil: IR (CHCl3) 3407, 2955, 2928, 2856, 1490, 1471, 1448, 1254, 1058, 1031, 836, 773, 705 cm−1; 1H NMR (300 MHz, CDCl3) ε7.57 (m, 6H), 7.37 (m, 9H), 5.78 (dd, J=15.6, 6.5 Hz, 1H), 5.73 (dt, J=15.5, 4.8 Hz, 1H), 3.91 (m, 1H), 3.82 (d, J=5.9 Hz, 2H), 3.69 (d, J=4.4 Hz, 2H), 2.51 (m, 1H), 2.22 (br, 1H), 1.77 (m, 2H), 1.13 (d, J=6.8 Hz, 3H), 1.03 (s, 9H), 0.21 (s, 3H), 0.19 (s, 3H); 13C NMR (75 MHz, CDCl3) δ 144.2, 134.1, 128.6, 127.7, 127.1, 126.9, 86.8, 74.3, 64.9, 60.4, 42.0, 34.8, 25.9, 18.0, 14.5, −4.4, −4.6; LRMS (ESI) 539.2 [M+Na]+, 243.2; HRMS (ESI) calcd for C33H44O3Si1Na 539.2957 [M+Na]+, found 539.2976; [α]20D−2.8 (c 2.0, CHCl3).

Workup

  1. customquenched with sat'd NaHCO3 (100 mL)
  2. customThe aqueous layer was separated
  3. extractionextracted with Et2O (3×50 mL)
  4. washThe combined organic layers were washed with sat'd CUSO4 (3×50 mL)
  5. dry with materialdried over MgSO4
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-ecfc075756174425b332e9c579e3b239
Source dataset
uspto-grants-2008_01
Patent number
US07321046B2

Reaction notes

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