Ethyl Acetate → HCID 57752554, compound

HRID 227189Notes

Reaction equation

HRID 227189 reaction equation
[CH2:1]([O:8][C:9]1[C:24]([O:25][CH3:26])=[CH:23][C:12]([C:13]([N:15]2[CH2:19][C@H:18]([OH:20])[CH2:17][C@H:16]2[CH2:21][OH:22])=[O:14])=[C:11]([N+:27]([O-])=O)[CH:10]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.O.O.Cl[Sn]Cl.CCOC(C)=O>CO>[NH2:27][C:11]1[CH:10]=[C:9]([O:8][CH2:1][C:2]2[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=2)[C:24]([O:25][CH3:26])=[CH:23][C:12]=1[C:13]([N:15]1[CH2:19][C@H:18]([OH:20])[CH2:17][C@H:16]1[CH2:21][OH:22])=[O:14]

Participants

5

Reactant 3

HCID 8857Ethyl AcetateHCID 61436Stannous chloride dihydrateHCID 57752559HCID 57752559, compound

Product 1

HCID 57752554HCID 57752554, compound

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

A mixture of diol 20 (26 g, 64.6 mmol, 1.0 equiv.) and SnCl2.2H2O (72.9 g, 323 mmol, 5.0 equiv.) in MeOH (300 mL), was heated at reflux and the progress of the reaction monitored by TLC (EtOAc). After 3 h, the MeOH was evaporated in vacuo and the resulting residue was cooled and treated carefully with saturated NaHCO3 (400 mL). The mixture was diluted with EtOAc (800 mL), and after 12 h stirring at room temperature the inorganic precipitate was removed by filtration through celite. The organic layer was separated, washed with brine (100 mL), dried (MgSO4), filtered and evaporated in vacuo to give a brown solid 21 which was used in the next reaction without further purification: [α]29D=−69° (c=0.13, CHCl3); 1H NMR (CDCl3, 400 MHz): δ 1.70-1.82 (m, 1H, 1-H), 2.06-2.19 (m, 1H, 1-H), 3.52-3.85 (m, 9H, 3-H, 11-H, 7-OMe, 2×OH), 4.26-4.72 (m, 1H, 11a-H), 4.47-4.60 (m, 1H, 2-H), 5.10 (s, 2H, OCH2Ph), 6.26 (s, 1H, 9-H), 6.78 (s, 1H, 6-H), 7.29-7.36 (m, 7H, Ph, NH2); 13C NMR (CDCl3, 100 MHz): δ 37.0, 57.1, 58.5, 59.0, 66.2, 69.4, 70.7, 103.4, 112.4, 112.9, 127.1, 128.0, 128.6, 136.5, 140.0, 141.9, 151.0, 172.8; IR (neat): 3358, 2939, 1619, 1589, 1512, 1455, 1432, 1408, 1263, 1231, 1171, 1113, 1012, 787, 735, 698, 644 cm−1; MS (ES+) m/z (relative intensity) 395 ([M+Na]+., 4), 373 ([M+H]+., 70), 374 ([M+2H]+., 40), 256 (100), 257 (45).

Workup

  1. temperaturewas heated
  2. temperatureat reflux
  3. customthe MeOH was evaporated in vacuo
  4. temperaturethe resulting residue was cooled
  5. additiontreated carefully with saturated NaHCO3 (400 mL)
  6. additionThe mixture was diluted with EtOAc (800 mL)
  7. customwas removed by filtration through celite
  8. customThe organic layer was separated
  9. washwashed with brine (100 mL)
  10. dry with materialdried (MgSO4)
  11. filtrationfiltered
  12. customevaporated in vacuo

Sources & evidence

ORD record
ord-89cd5e39b8f147e48c53340e812a031b
Source dataset
uspto-grants-2009_07
Patent number
US07557099B2

Reaction notes

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