Hydrochloric Acid → HCID 24766759, compound

HRID 2252492Notes

Reaction equation

HRID 2252492 reaction equation
Cl.[Si]([O:9][C@@H:10]([CH2:20][C@H:21]([O:61][Si](C(C)(C)C)(C)C)/[CH:22]=[CH:23]\[C@H:24]([CH3:60])[C@H:25]([O:52][Si](C(C)(C)C)(C)C)[C@@H:26]([CH3:51])[CH2:27][C@@H:28]([CH3:50])[CH2:29][CH2:30][C@@H:31]([O:42][Si](C(C)(C)C)(C)C)[C@H:32]([CH3:41])[C@@H:33]([OH:40])[C@@H:34]([CH3:39])/[CH:35]=[CH:36]\[CH:37]=[CH2:38])[C@H:11]([CH3:19])/[CH:12]=[CH:13]/[CH:14]=C\C(O)=O)(C(C)(C)C)(C)C.C[CH2:70][O:71][C:72]([CH3:74])=[O:73]>C1COCC1.O>[CH3:70][O:71][C:72](=[O:73])/[CH:74]=[CH:14]\[CH:13]=[CH:12]\[C@@H:11]([CH3:19])[C@@H:10]([OH:9])[CH2:20][C@H:21]([OH:61])/[CH:22]=[CH:23]\[C@H:24]([CH3:60])[C@H:25]([OH:52])[C@@H:26]([CH3:51])[CH2:27][C@@H:28]([CH3:50])[CH2:29][CH2:30][C@@H:31]([OH:42])[C@H:32]([CH3:41])[C@@H:33]([OH:40])[C@@H:34]([CH3:39])/[CH:35]=[CH:36]\[CH:37]=[CH2:38]

Participants

6

Reactant 3

HCID 313Hydrochloric AcidHCID 8857Ethyl AcetateHCID 66572241HCID 66572241, compound

Product 1

HCID 24766759HCID 24766759, compoundYield 36%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Procedure

3N HCl (10 mL, prepared by adding 2.5 mL of conc. HCl to 7.5 mL MeOH) was added to a stirred solution of the macrolactonization precursor 48 (23 mg, 23 μmol) in THF (3 mL) at 0° C. After 24 h at room temperature, the reaction mixture was diluted with EtOAc (4 mL) and H2O (4 mL). The organic phase was retained and aqueous phase was extracted with EtOAc (2×4 mL). The combined organic phase was washed with saturated aqueous NaHCO3 (10 mL), dried with MgSO4, filtered and concentrated. The residue was purified by flash chromatography (EtOAc/hexane 3:2) to yield the product 50 (4.5 mg, 36%) as a colorless oil: IR (CHCl3) 3399, 2917, 2849, 1713, 1635, 1600, 1461, 1439, 1197, 1178, 970, 757 cm−1; 1H NMR (600 MHz, CD3OD) δ 7.36 (dd, J=15.3, 11.2 Hz, 1H), 6.67 (ddd, J=16.9, 11.1, 10.6 Hz, 1H), 6.63 (dd, J=11.3, 11.3 Hz, 1H), 6.14 (dd, J=15.4, 8.3 Hz, 1H), 6.03 (dd, J=11.0, 1.0 Hz, 1H), 5.59 (d, J=11.4 Hz, 1H), 5.43 (dd, J=10.7, 10.7 Hz, 1H), 5.42 (dd, J=10.8, 9.2 Hz, 1H), 5.32 (dd, J=10.4, 10.4 Hz, 1H), 5.17 (dd, J=16.8, 2.0 Hz, 1H), 5.08 (d, J=10.2 Hz, 1H), 4.61 (ddd, J=12.9, 8.5, 4.6 Hz, 1H), 3.80 (ddd, J=8.9, 4.4, 4.4 Hz, 1H), 3.69 (s, 3H), 3.63 (m, 1H), 3.46 (t, J=5.8 Hz, 1H), 3.13 (dd, J=8.0, 3.2 Hz, 1H), 2.93 (m, 1H), 2.71 (m, 1H), 2.38 (m, 1H), 1.73 (m, 1H), 1.56-1.53 (m, 3H), 1.52-1.46 (m, 2H), 1.44-1.36 (m, 3H), 1.09 (d, J=6.9 Hz, 3H), 0.98 (d, J=6.8 Hz, 3H), 0.96 (d, J=6.6 Hz, 3H), 0.95 (m, 2H), 0.94 (d, J=6.9 Hz, 3H), 0.87 (d, J=6.6 Hz, 3H), 0.86 (d, J=6.8 Hz, 3H); 13C NMR (150 MHz, CD3OD) δ 168.4, 148.5, 146.9, 135.7, 135.4, 133.85, 133.82, 130.6, 128.2, 117.7, 116.2, 79.2, 78.5, 74.8, 72.4, 65.8, 51.5, 45.1, 43.2, 43.0, 41.0, 37.2, 36.5, 34.0, 33.3, 33.1, 31.0, 20.7, 18.6, 18.4, 16.7, 13.8, 7.8; LRMS (ESI) 587.5 [M+Na]+, 559.2, 485.2, 413.3, 355.1, 212.1; HRMS (ESI) calcd for C33H56O7Na 587.3924 [M+Na]+, found 587.3953; [α]20D+8.7 (c 0.30, CDCl3).

Workup

  1. extractionaqueous phase was extracted with EtOAc (2×4 mL)
  2. washThe combined organic phase was washed with saturated aqueous NaHCO3 (10 mL)
  3. dry with materialdried with MgSO4
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customThe residue was purified by flash chromatography (EtOAc/hexane 3:2)

Sources & evidence

ORD record
ord-3d12c4083c064d71a4c956b660528f4d
Source dataset
uspto-grants-2008_01
Patent number
US07321046B2

Reaction notes

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