Sodium Bicarbonate → HCID 66916261, compound

HRID 227191Notes

Reaction equation

HRID 227191 reaction equation
C1COCC1.CC(O)=O.O.[C:11]([O:15][C:16]([N:18]1[C:24]2[CH:25]=[C:26]([O:31]C3C(O)=C(O)C(O)=C(O)O3)[C:27]([O:29][CH3:30])=[CH:28][C:23]=2[C:22](=[O:42])[N:21]2[CH2:43][C:44](=[CH2:46])[CH2:45][C@H:20]2[C@@H:19]1[O:47][CH:48]1[C:53]([OH:54])=[C:52]([OH:55])[C:51]([OH:56])=[C:50]([OH:57])[O:49]1)=[O:17])([CH3:14])([CH3:13])[CH3:12].C([O-])(O)=O.[Na+]>CCOC(C)=O.CCCCCC>[C:11]([O:15][C:16]([N:18]1[C:24]2[CH:25]=[C:26]([OH:31])[C:27]([O:29][CH3:30])=[CH:28][C:23]=2[C:22](=[O:42])[N:21]2[CH2:43][C:44](=[CH2:46])[CH2:45][C@H:20]2[C@@H:19]1[O:47][CH:48]1[C:53]([OH:54])=[C:52]([OH:55])[C:51]([OH:56])=[C:50]([OH:57])[O:49]1)=[O:17])([CH3:14])([CH3:12])[CH3:13]

Participants

5

Reactant 3

HCID 516892Sodium BicarbonateHCID 21877175AcOH THF waterHCID 69018403HCID 69018403, compound

Product 1

HCID 66916261HCID 66916261, compoundYield 87.9%

Reagents, catalysts & solvents 1

HCID 21226206Ethyl acetate hexaneSolvent2×

Procedure

A solution of THF/AcOH/H2O (2:1:1, 5 mL) was added to the olefin 26 (1.8 g, 3.3 mmol) and the resulting mixture was stirred for 3 h at which point TLC (SiO2, 50% EtOAc-hexane) revealed complete reaction. The mixture was then neutralized with saturated NaHCO3 and extracted with EtOAc (3×30 mL) and the combined organic layers were washed with brine (50 mL) and dried (MgSO4). Removal of excess solvent under reduced pressure gave the crude product. The residue was subjected to flash chromatography (SiO2, 50% EtOAc-hexane) to afford the product 27 (1.34 g, 2.9 mmol, 87% yield, mixture of diastereomers from THP protecting group): [α]27D=+81° (c=0.16, CHCl3); 1H NMR (CDCl3, 400 MHz): δ 1.32 (s, 18H, Boc), 1.45-1.64 (m, 8H, THP), 1.66-1.84 (m, 4H, THP), 2.50-2.58 (m, 1H, 1-H), 2.68-2.80 (m, 1H, 1-H), 2.84-2.96 (m, 2H, 1-H), 3.51-3.67 (m, 4H, 11a-H, THP), 3.87-4.00 (m, 8H, 7-OMe, THP), 4.04-4.18 (m, 2H, 3-H), 4.23-4.38 (m, 2H, 3-H), 4.96-5.19 (m, 6H, 2a-H, THP), 5.65-5.72 (d, 1H, 11-H), 5.75-5.88 (d, 1H, 11-H), 5.97 (s, 1H, 8-OH), 6.00 (s, 1H, 8-OH), 6.63 (s, 1H, 9-H), 6.92 (s, 1H, 9-H), 7.17 (s, 1H, 6-H), 7.21 (s, 1H, 6-H); 13C NMR (CDCl3, 100 MHz): δ 20.0, 20.7, 25.1, 25.2, 28.0, 28.1, 29.7, 30.8, 31.3, 35.1, 35.4, 50.7, 56.1, 56.2, 59.8, 60.0, 63.6, 64.6, 88.0, 91.0, 96.1, 100.7, 109.4, 109.8, 116.4, 117.0, 130.3, 130.5, 142.0, 145.8, 146.0, 147.5, 147.7, 167.3, 167.5; IR (neat): 2940, 2851, 1703, 1630, 1512, 1467, 1440, 1407, 1391, 1367, 1326, 1200, 1161, 1118, 1072, 1019, 910, 730 cm−1; MS (ES+) m/z (relative intensity) 461 (M+., 75), 462 ([M+2H]+., 20), 259 (100), 260 (30), 359 (21).

Workup

  1. customreaction
  2. extractionextracted with EtOAc (3×30 mL)
  3. washthe combined organic layers were washed with brine (50 mL)
  4. dry with materialdried (MgSO4)
  5. customRemoval of excess solvent under reduced pressure
  6. customgave the crude product

Sources & evidence

ORD record
ord-246494bd383943ccb001f249c3f4bf2c
Source dataset
uspto-grants-2009_07
Patent number
US07557099B2

Reaction notes

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