Pyridine, hydrofluoride (1:1) → HCID 86602907, compound

HRID 2252506Notes

Reaction equation

HRID 2252506 reaction equation
C1C=CN=CC=1.F.[Si:8]([O:15][C@@H:16]([CH2:42][C@H:43]([O:71][Si:72]([C:75]([CH3:78])([CH3:77])[CH3:76])([CH3:74])[CH3:73])/[CH:44]=[CH:45]\[C@H:46]([CH3:70])[C@H:47]([O:62][Si:63]([C:66]([CH3:69])([CH3:68])[CH3:67])([CH3:65])[CH3:64])[C@H:48]([CH3:61])[CH2:49][C@@H:50]([CH3:60])[CH2:51][O:52][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:63]([O:62][C@@H:47]([C@@H:46]([CH3:70])/[CH:45]=[CH:44]\[C@@H:43]([O:71][Si:72]([C:75]([CH3:78])([CH3:76])[CH3:77])([CH3:74])[CH3:73])[CH2:42][C@H:16]([O:15][Si:8]([C:11]([CH3:14])([CH3:13])[CH3:12])([CH3:10])[CH3:9])[C@@H:17]([CH3:41])/[CH:18]=[CH:19]/[CH2:20][O:21][C:22]([C:29]1[CH:30]=[CH:31][CH:32]=[CH:33][CH:34]=1)([C:23]1[CH:24]=[CH:25][CH:26]=[CH:27][CH:28]=1)[C:35]1[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=1)[C@H:48]([CH3:61])[CH2:49][C@@H:50]([CH3:60])[CH2:51][OH:52])([C:66]([CH3:69])([CH3:67])[CH3:68])([CH3:65])[CH3:64]

Participants

5

Reactant 2

HCID 64774Pyridine, hydrofluoride (1:1)HCID 86602908HCID 86602908, compound

Product 1

HCID 86602907HCID 86602907, compoundYield 66%

Reagents, catalysts & solvents 2

HCID 1049PyridineSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

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 slowly added to a solution of TBS ether 87 (3.54 g, 4.10 mmol) in THF (5 mL) at 0° C. The mixture was stirred for 2 days at 0° C. 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 15:85) afforded 2.08 g (66%) of the alcohol as a colorless oil: IR (CHCl3) 3400, 2956, 2928, 2856, 1471, 1448, 1254, 1075, 836, 773 cm−1; 1H NMR (300 MHz, CDCl3) δ 7.52-7.48 (m, 6H), 7.36-7.24 (m, 9H), 5.87 (dd, J=15.7, 5.9 Hz, 1H), 5.59 (dt, J=15.7, 5.7 Hz, 1H), 5.55 (dd, J=10.6, 10.4 Hz, 1H), 5.33 (dd, J=11.0, 8.7 Hz, 1H), 4.58 (m, 1H), 3.94 (m, 1H), 3.60 (d, J=5.5 Hz, 2H), 3.38-3.32 (m, 2H), 3.25 (m, 1H), 2.62 (m, 1H), 2.45 (m, 1H), 1.59 (m, 1H), 1.55 (m, 1H), 1.47 (m, 1H), 1.35 (m, 1H), 1.09 (m, 1H), 1.04 (d, J=7.6 Hz, 3H), 1.01 (d, J=7.2 Hz, 3H), 0.96 (s, 9H), 0.94 (s, 9H), 0.93 (s, 9H), 0.79 (d, J=6.8 Hz, 3H), 0.75 (d, J=6.6 Hz, 3H), 0.15 (s, 9H), 0.14 (s, 3H), 0.10 (s, 3H), 0.09 (s, 3H), 0.08 (s, 3H), 0.07 (s, 3H); 13C NMR (75 MHz, CDCl3) δ 144.4, 134.0, 132.7, 131.3, 128.7, 127.7, 126.8, 126.5, 86.8, 81.0, 73.0, 69.2, 66.5, 65.3, 42.6, 42.2, 36.2, 35.5, 34.6, 33.3, 26.2, 26.1, 25.9, 20.0, 18.4, 18.2, 18.1, 15.7, 15.6, 14.9, −2.8, −3.7, −3.8, −4.0, −4.1, −4.2; LRMS (ESI) 951.6 [M+Na]+, 705.1, 631.1, 557.0, 397.2, 381.2, 353.2, 243.1; HRMS (ESI) calcd for C56H92O5Si3Na 951.6150 [M+Na]+, found 951.6158; [α]20D−33.5 (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-03dfdb2510704c9f9c0f8f83dac1c21b
Source dataset
uspto-grants-2008_01
Patent number
US07321046B2

Reaction notes

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