HCID 131729470, compound → HCID 131729469, compound

HRID 1644791Notes

Reaction equation

HRID 1644791 reaction equation
[C:1]([NH:4][C@@H:5]1[C@@H:10]([O:11][C:12](=[O:14])[CH3:13])[C@H:9]([O:15][C:16](=[O:18])[CH3:17])[C@@H:8]([CH2:19][O:20][C:21](=[O:23])[CH3:22])[O:7][C@H:6]1[O:24][C@@H:25]1[C@H:34]([O:35][CH2:36][C:37]2[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=2)[C@@H:33]([O:43][CH2:44][C:45]2[CH:50]=[CH:49][CH:48]=[CH:47][CH:46]=2)[C@H:32]([CH3:51])[O:31][C@H:26]1[O:27]CC=C)(=[O:3])[CH3:2]>C1COCC1>[C:1]([NH:4][C@@H:5]1[C@@H:10]([O:11][C:12](=[O:14])[CH3:13])[C@H:9]([O:15][C:16](=[O:18])[CH3:17])[C@@H:8]([CH2:19][O:20][C:21](=[O:23])[CH3:22])[O:7][C@H:6]1[O:24][C@@H:25]1[C@H:34]([O:35][CH2:36][C:37]2[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=2)[C@@H:33]([O:43][CH2:44][C:45]2[CH:50]=[CH:49][CH:48]=[CH:47][CH:46]=2)[C@H:32]([CH3:51])[O:31][C@H:26]1[OH:27])(=[O:3])[CH3:2]

Participants

3

Reactant 1

HCID 131729470HCID 131729470, compound

Product 1

HCID 131729469HCID 131729469, compoundYield 69.2%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

1,5-Cyclooctadiene-bis(methyldiphenylphosphine)iridium hexafluorophosphate (10 mg, 12 μmol) was dissolved THF (10 mL), and the resulting red solution was degassed in an argon stream. Hydrogen was then bubbled through the solution, causing the colour to change to yellow. The solution was then degassed again in an argon stream. A solution of 319 (830 mg, 1.16 mmol) in THF (40 mL) was degassed and added. The mixture was stirred at rt overnight. The mixture was concentrated. The residue was taken up in acetone (90 mL), and water (10 mL) was added. Mercuric chloride (475 mg, 1.75 mmol) and mercuric oxide (504 mg, 2.32 mmol) were added to the mixture, protected from light. The mixture was stirred for 2 h at rt, 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 (cyclohexane-EtOAc 3:7) to give 320 (541 mg, 69%) as a white foam; [α]D+16° (c 1.0, CHCl3); 1H NMR: δ 7.35-7.05 (m, 10H, Ph), 5.50 (d, 1H, J2,NH=8.2 Hz, NHD), 5.22 (d, 1H, J1,2=1.1 Hz, H-1A), 5.06 (pt, 1H, J3,4=J4,5=9.5 Hz, H-4D), 5.00 (pt, 1H, J2,3=9.5 Hz, H-3D), 4.85-4.60 (m, 4H, CH2Ph), 4.56 (d, 1H, J1,2=7.0 Hz, H-1D), 4.22-4.13 (m, 2H, J5,6=4-5, J6a,6b=12.3 Hz, H-6aD, 6bD), 4.03 (m, 1H, H-2D), 4.00 (dq, 1H, J4,5=9.5, J5,6=6.2 Hz, H-5A), 3.96 (dd, 1H, J2,3=3.3 Hz, H-2A), 3.90 (dd, 1H, J3,4=9.5 Hz, H-3A), 3.60 (m, 1H, H-5D), 3.48 (d, 1H, J1,OH=3.5 Hz, OH), 3.40 (pt, 1H, H-4A), 2.08, 2.03, 2.01 (3s, 9H, OAc), 1.65 (s, 3H, NHAc), 1.30 (d, 3H, H-6A); 13C NMR: δ 171.2, 171.0, 170.4, 169.6 (C═O), 138.2-128.0 (Ph), 103.3 (C-1D), 94.1 (C-1A), 81.4 (C-4A), 79.9 (C-2A), 78.7 (C-3A), 75.8, 73.9 (2C, CH2Ph), 73.6 (C-3D), 72.4 (C-5D), 68.7 (C-4D), 68.2 (C-5A), 62.4 (C-6D), 54.5 (C-2D), 23.3 (NHAc), 21.1, 21.0, 21.0 (3C, OAc), 18.3 (C-6A). FAB-MS for C34H43NO13 (M, 673.2), m/z 696.3 [M+Na]+. Anal Calcd for C34H43NO13: C, 60.61; H, 6.43; N, 2.08. Found: C, 60.46; H, 6.61; N, 1.95.

Workup

  1. customthe resulting red solution was degassed in an argon stream
  2. customHydrogen was then bubbled through the solution
  3. customThe solution was then degassed again in an argon stream
  4. additionadded
  5. concentrationThe mixture was concentrated
  6. additionwater (10 mL) was added
  7. stirringThe mixture was stirred for 2 h at rt
  8. concentrationconcentrated
  9. washwashed three times with sat. aq. KI
  10. customThe organic phase was dried
  11. concentrationconcentrated
  12. customThe residue was purified by column chromatography (cyclohexane-EtOAc 3:7)

Sources & evidence

ORD record
ord-8068833779a44d16814105422c9d5730
Source dataset
uspto-grants-2012_02
Patent number
US08124380B2

Reaction notes

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