HCID 131729467, compound → HCID 131729466, compound

HRID 62289Notes

Reaction equation

HRID 62289 reaction equation
[C:1]([O:4][C@H:5]1[C@H:10]([O:11][C:12](=[O:14])[CH3:13])[C@@H:9]([CH2:15][O:16][C:17](=[O:19])[CH3:18])[O:8][C@@H:7]([O:20][C@@H:21]2[C@H:30]([O:31][CH2:32][C:33]3[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=3)[C@@H:29]([O:39][CH2:40][C:41]3[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=3)[C@H:28]([CH3:47])[O:27][C@H:22]2[O:23]CC=C)[C@@H:6]1[NH:48][C:49](=[O:54])[C:50]([Cl:53])([Cl:52])[Cl:51])(=[O:3])[CH3:2]>O1CCCC1>[C:1]([O:4][C@H:5]1[C@H:10]([O:11][C:12](=[O:14])[CH3:13])[C@@H:9]([CH2:15][O:16][C:17](=[O:19])[CH3:18])[O:8][C@@H:7]([O:20][C@@H:21]2[C@H:30]([O:31][CH2:32][C:33]3[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=3)[C@@H:29]([O:39][CH2:40][C:41]3[CH:42]=[CH:43][CH:44]=[CH:45][CH:46]=3)[C@H:28]([CH3:47])[O:27][C@H:22]2[OH:23])[C@@H:6]1[NH:48][C:49](=[O:54])[C:50]([Cl:53])([Cl:52])[Cl:51])(=[O:3])[CH3:2]

Participants

3

Reactant 1

HCID 131729467HCID 131729467, compound

Product 1

HCID 131729466HCID 131729466, compoundYield 83.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

1,5-Cyclooctadiene-bis(methyldiphenylphosphine)iridium hexafluorophosphate (120 mg, 140 μmol) was dissolved tetrahydrofuran (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 317 (1.46 g, 1.75 mmol) in tetrahydrofuran (20 mL) was degassed and added. The mixture was stirred at rt overnight. The mixture was concentrated. The residue was taken up in acetone (27 mL), and water (3 mL) was added. Mercuric bromide (949 mg, 2.63 mmol) and mercuric oxide (761 mg, 3.5 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 limes with sat. aq. KI, then with brine. The organic phase was dried and concentrated. The residue was purified by column chromatography (cyclohexane-EtOAc 4:1) to give 318 (1.13 g, 81%) as a white foam. [α]D+4° (c 1, CHCl3). 1H NMR: δ 7.35-7.05 (m, 10H, Ph), 6.74 (d, 1H, J2,NH=8.5 Hz, NHD), 5.10 (d, 1H, J1,2=1.1 Hz, H-1A), 5.02 (m, 2H, H-3D, 4D), 4.80-4.50 (m, 4H, CH2Ph), 4.61 (d, 1H, J1,2=8.5 Hz, H-1D), 4.15-4.08 (m, 2H, J5,6=4.5, J6a,6b=12.3 Hz, H-6aD, 6bD), 4.00 (m, 1H, H-2D), 3.90 (dd, 1H, J2,3=3.3, H-2A), 3.86 (dd, 1H, J3,4=9.5 Hz, H-3A), 3.85 (dq, 1H, J4,5=9.5, J5,6=6.2 Hz, H-5A), 3.50 (m, 1H, H-5D), 3.30 (pt, 1H, H-4A), 2.85 (d, 1H, J1,OH=3.5 Hz, OH), 2.02, 1.97, 1.94 (3s, 9H, OAc), 1.23 (d, 3H, H-6A); 13C NMR: δ 171.1, 170.0, 169.6, 162.1 (C═O), 138.5-127.1 (Ph), 101.7 (C-1D), 94.1 (C-1A), 92.6 (CCl3), 81.4 (C-4A), 79.9 (C-2A), 77.3 (C-3A), 75.9, 74.1 (2C, CH2Ph), 72.7 (C-3D), 72.5 (C-5D), 68.6 (C-4D), 68.4 (C-5A), 62.2 (C-6D), 56.1 (C-2D), 21.1, 21.0, 20.9 (3C, OAc), 18.3 (C-6A). FAB-MS for C34H40Cl3NO13 (M, 775), m/z 789 [M+Na]+. Anal. Calcd for C34H40Cl3NO13: C, 52.55; H, 5.19; N, 1.80%. Found: C, 52.48; H, 5.37; N, 1.67%.

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 (3 mL) was added
  7. stirringThe mixture was stirred for 2 h at rt
  8. concentrationconcentrated
  9. washwashed three limes with sat. aq. KI
  10. customThe organic phase was dried
  11. concentrationconcentrated
  12. customThe residue was purified by column chromatography (cyclohexane-EtOAc 4:1)

Sources & evidence

ORD record
ord-ba7f4395193f4e25951c5c8d31735944
Source dataset
uspto-grants-2016_09
Patent number
US09446109B2

Reaction notes

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