HCID 21585607, compound → HCID 21585608, compound

HRID 1644796Notes

Reaction equation

HRID 1644796 reaction equation
[C:1]([O:9][C@@H:10]1[C@H:15]([O:16][C:17](=[O:24])[C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[C@@H:14]([O:25][C:26](=[O:33])[C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)[C@H:13]([CH3:34])[O:12][C@H:11]1[O:35][C@@H:36]1[C@H:45]([O:46][CH2:47][C:48]2[CH:53]=[CH:52][CH:51]=[CH:50][CH:49]=2)[C@@H:44]([O:54][CH2:55][C:56]2[CH:61]=[CH:60][CH:59]=[CH:58][CH:57]=2)[C@H:43]([CH3:62])[O:42][C@H:37]1[O:38]CC=C)(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1>C1COCC1>[C:1]([O:9][C@@H:10]1[C@H:15]([O:16][C:17](=[O:24])[C:18]2[CH:19]=[CH:20][CH:21]=[CH:22][CH:23]=2)[C@@H:14]([O:25][C:26](=[O:33])[C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)[C@H:13]([CH3:34])[O:12][C@H:11]1[O:35][C@@H:36]1[C@H:45]([O:46][CH2:47][C:48]2[CH:49]=[CH:50][CH:51]=[CH:52][CH:53]=2)[C@@H:44]([O:54][CH2:55][C:56]2[CH:57]=[CH:58][CH:59]=[CH:60][CH:61]=2)[C@H:43]([CH3:62])[O:42][C@H:37]1[OH:38])(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

3

Reactant 1

HCID 21585607HCID 21585607, compound

Product 1

HCID 21585608HCID 21585608, compoundYield 86.2%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

1,5-Cyclooctadiene-bis(methyldiphenylphosphine)iridium hexafluorophosphate (25 mg) was dissolved in THF (10 mL) and the resulting red solution was degassed in an argon stream. Hydrogen was then bubbled through the solution, until the colour had changed to yellow. The solution was then degassed again in an argon stream. A solution of 528 (4.71 g, 5.59 mmol) in THF (40 mL) was degassed and added. The mixture was stirred at rt overnight, then concentrated. The residue was taken up in acetone (350 mL) and water (82 mL). Mercuric bromide (3.23 g, 8.96 mmol) and mercuric oxide (2.64 g, 12.3 mmol) were added to the mixture, which was protected from light. The suspension was stirred at rt for 1 h, then concentrated. The residue was taken up in CH2Cl2 and washed three times with sat aq KI, then with brine. The organic phase was dried and concentrated. The residue was purified by column chromatography (solvent B, 3:1) to give 529 (3.87 g, 84%) as a colourless foam. 1H NMR: δ 8.15-7.12 (m, 25H, Ph), 5.94-5.88 (m, 3H, H-2A, 3A, CH═), 5.70 (pt, 1H, J3,4=9.7 Hz, H-4A), 5.31 (dd, 1H, J1,OH=3.0 Hz, H-1B), 5.28 (bs, 1H, H-1A), 4.98 (d, 1H, J=11.0 Hz, CH2Ph), 4.82-4.68 (m, 3H, CH2Ph), 4.31 (dq, 1H, J4,5=9.8 Hz, H-5A), 4.13 (dd, 1H, J1,2=2.1 Hz, H-2B), 4.06-3.99 (m, 2H, H-3B, 5B), 3.72 (pt, 1H, J3,4=J4,5=9.4 Hz, H-4B), 2.79 (bs, 1H, OH-1B), 1.41 (d, 3H, J5,6=6.2 Hz, H-6B), 1.37 (d, 3H, J5,6=6.3 Hz, H-6A); 13C NMR: δ 166.2, 165.9, 165.7 (3C, C═O), 138.9-127.9 (Ph), 99.7 (C-1A), 94.2 (C-1B), 80.5 (C-4B), 79.6 (C-3B), 77.6 (C-2B), 76.5, 72.5 (2C, CH2Ph), 72.3 (C-4A), 71.0 (C-2A*), 70.4 (C-3A*), 68.8 (C-5B), 67.6 (C-5A), 18.5 (C-6B*), 18.1 (C-6A*). FAB-MS for C47H46O12 (M, 802.3) m/z 825.1 [M+Na]+. Anal. Calcd. for C47H46O12.0.5H2O: C, 69.53; H, 5.84%. Found C, 69.55; H, 5.76%.

Workup

  1. customthe resulting red solution was degassed in an argon stream
  2. customHydrogen was then bubbled through the solution, until the colour
  3. customThe solution was then degassed again in an argon stream
  4. additionadded
  5. concentrationconcentrated
  6. stirringThe suspension was stirred at rt for 1 h
  7. concentrationconcentrated
  8. washwashed three times
  9. customThe organic phase was dried
  10. concentrationconcentrated
  11. customThe residue was purified by column chromatography (solvent B, 3:1)

Sources & evidence

ORD record
ord-f638bfaa0e5744ff85eec7696daddde6
Source dataset
uspto-grants-2012_02
Patent number
US08124380B2

Reaction notes

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