Water → HCID 44629274, compound

HRID 731117Notes

Reaction equation

HRID 731117 reaction equation
[Si]([O:8][C@H:9]([C:17]#[C:18]/[CH:19]=[CH:20]/[CH:21]=[CH:22]/[C@H:23]([O:40][Si](C(C)(C)C)(C)C)[CH2:24][C:25]#[C:26]/[CH:27]=[CH:28]/[C@H:29]([O:32][Si](C(C)(C)C)(C)C)[CH2:30][CH3:31])[CH2:10][CH2:11][CH2:12][C:13]([O:15][CH3:16])=[O:14])(C(C)(C)C)(C)C.CCCC[N+](CCCC)(CCCC)CCCC.[F-].O>C1COCC1>[OH:8][C@H:9]([C:17]#[C:18]/[CH:19]=[CH:20]/[CH:21]=[CH:22]/[C@H:23]([OH:40])[CH2:24][C:25]#[C:26]/[CH:27]=[CH:28]/[C@H:29]([OH:32])[CH2:30][CH3:31])[CH2:10][CH2:11][CH2:12][C:13]([O:15][CH3:16])=[O:14]

Participants

5

Reactant 3

HCID 962WaterHCID 2724141Tetrabutylammonium FluorideHCID 44629273HCID 44629273, compound

Product 1

HCID 44629274HCID 44629274, compoundYield 90%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A solution of the product of Example 4 (40 mg, 0.065 mmol) in THF (1 ml) was treated with 1.0 M TBAF (0.32 ml, 0.32 mmol) at 0° C. The reaction was stirred for 3 h and then poured into water and extracted with ether. The ether extracts were washed with brine, dried and concentrated. The ethereal solution was then treated with an excess of freshly prepared diazomethane in ether to convert the free acid to the product. Flash column chromatography (silica gel, 4% MeOH/CH2Cl2) afforded the pure product in 90% yield. 1H NMR (500 MHz, C6D6): δ 6.55 (dd, J=15.5 Hz and 10.9 Hz, 1H), 6.16 (dd, J=15.2 Hz and 11.0 Hz, 1H), 6.05 (dd, J=15.5 Hz and 5.3 Hz, 1H), 5.70 (d, J=16.2 Hz, 1H), 5.61 (dd, J=14.6 Hz and 5.5 Hz, 1H), 5.58 (d, J=14.7 Hz, 1H), 4.28 (t, J=5.8 Hz, 1H), 4.06 (dd, J=11.2 Hz and 5.3 Hz, 1H), 3.65 (dd, J=1.0 Hz and 6.7 Hz, 1H), 3.30 (s, 3H), 2.36 (m, 2H), 2.06 (t, J=6.9 Hz, 2H), 1.72 (m, 2H), 1.59 (m, 2H), 1.27 (m, 2H), 0.74 (t, J=7.4 Hz, 3H). 13C NMR (125 MHz, C6D6): δ 173.819, 145.219, 141.143, 136.647, 130.007, 111.340, 109.915, 92.672, 85.857, 84.082, 81.330, 73.505, 70.225, 62.533, 51.488, 37.097, 33.599, 29.912, 28.658, 20.615, 9.451. HPLC: Beckman Ultrasphere reverse phase column (30% water in MeOH, 3.8 ml/min, 252 bar): elution time=5.41 min.

Workup

  1. extractionextracted with ether
  2. washThe ether extracts were washed with brine
  3. customdried
  4. concentrationconcentrated
  5. additionThe ethereal solution was then treated with an excess of freshly prepared diazomethane in ether
  6. customFlash column chromatography (silica gel, 4% MeOH/CH2Cl2) afforded the pure product in 90% yield
  7. washHPLC: Beckman Ultrasphere reverse phase column (30% water in MeOH, 3.8 ml/min, 252 bar): elution time=5.41 min.

Sources & evidence

ORD record
ord-4a16464e5f5441588a0da2d1f8bc1f52
Source dataset
uspto-grants-2009_09
Patent number
US07582785B2

Reaction notes

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