Pyridine → HCID 87277103, compound

HRID 406163Notes

Reaction equation

HRID 406163 reaction equation
[OH:1][C:2]1[C:7]2[C@@:8]3([OH:46])[C@@:21]([O:25][CH3:26])([C@H:22]([OH:24])[CH2:23][C:6]=2[CH:5]=[C:4]([CH3:47])[C:3]=1[C:48]([O:50][CH3:51])=[O:49])[C:20](=[O:27])[C:19]1[C:10](=[CH:11][C:12]2[C:13](=[O:44])[C:14]([NH:30][C@@H:31]4[C@H:36]([O:37][CH3:38])[C:35](=[N:39][OH:40])[C@@H:34]([O:41][CH3:42])[C@H:33]([CH3:43])[O:32]4)=[CH:15][C:16](=[O:29])[C:17]=2[C:18]=1[OH:28])[C:9]3=[O:45].[N:52]1C=CC=[CH:54][CH:53]=1>CO>[NH2:52][CH2:53][CH2:54][O:40]/[N:39]=[C:35]1\[C@@H:36]([O:37][CH3:38])[C@@H:31]([NH:30][C:14]2[C:13](=[O:44])[C:12]3[CH:11]=[C:10]4[C:19]([C:20](=[O:27])[C@@:21]5([O:25][CH3:26])[C@@:8]([OH:46])([C:9]4=[O:45])[C:7]4[C:2]([OH:1])=[C:3]([C:48]([O:50][CH3:51])=[O:49])[C:4]([CH3:47])=[CH:5][C:6]=4[CH2:23][C@H:22]5[OH:24])=[C:18]([OH:28])[C:17]=3[C:16](=[O:29])[CH:15]=2)[O:32][C@@H:33]([CH3:43])[C@@H:34]\1[O:41][CH3:42]

Participants

4

Reactant 2

HCID 1049PyridineHCID 86660839HCID 86660839, compound

Product 1

HCID 87277103HCID 87277103, compoundYield 33%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

To a solution of the ketone from Step A of the preparation of (6R,6aS,14aR)-methyl 1,6,8,14a-tetrahydroxy-11-((2S,3R,5R,6S)-4-(hydroxyimino)-3,5-dimethoxy-6-methyltetrahydro-2H-pyran-2-ylamino)-6a-methoxy-3-methyl-7,9,12,14-tetraoxo-5,6,6a,7,9,12,14,14a-octahydrobenzo[a]tetracene-2-carboxylate [Isomer A](Example 48) (50 mg, 0.072 mmol) in methanol (1 mL) was added 2-(aminooxy)-1-ethanaminum dihydrochloride (10.7 mg, 0.072 mmol) and pyridine (0.1 mL) at room temperature. The mixture was stirred under nitrogen for 6 h. The reaction mixture was quenched with a saturated solution of sodium bicarbonate and extracted with ethyl acetate. The combined extracts were washed with brine, dried (Na2SO4), filtered and concentrated. The residue was purified by preparative TLC (silica gel, 90:10 chloroform/methanol) to afford (6R,6aS,14aR)-methyl 11-((2S,3R,5R,6S,Z)-4-(2-aminoethoxyimino)-3,5-dimethoxy-6-methyltetrahydro-2H-pyran-2-ylamino)-1,6,8,14a-tetrahydroxy-6a-methoxy-3-methyl-7,9,12,14-tetraoxo-5,6,6a,7,9,12,14,14a-octahydrobenzo[a]tetracene-2-carboxylate (18 mg, 33%) as a brown solid: 1H NMR (500 MHz, CDCl3) δ 8.20 (s, 1H), 7.00 (br s, 1H), 6.53 (s, 1H), 5.93 (s, 1H), 4.98 (d, J=1.5 Hz, 1H), 4.95 (d, J=6.0 Hz, 1H), 4.87 (br s, 1H), 4.29-4.26 (m, 3H), 3.83 (s, 3H), 3.74-3.70 (m, 2H), 3.61-3.54 (m, 2H), 3.58 (s, 3H), 3.47 (s, 3H), 3.40 (s, 3H), 3.34 (d, J=19.5 Hz, 1H), 3.11-3.06 (m, 2H), 2.40 (s, 3H), 1.37 (d, J=6.0 Hz, 3H), 1.24 (t, J=7.0 Hz, 2H); MS (ESI+) m/z 754 (M+H); HPLC 95.6% (AUC), tR 10.86 min.

Workup

  1. customThe reaction mixture was quenched with a saturated solution of sodium bicarbonate
  2. extractionextracted with ethyl acetate
  3. washThe combined extracts were washed with brine
  4. dry with materialdried (Na2SO4)
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe residue was purified by preparative TLC (silica gel, 90:10 chloroform/methanol)

Sources & evidence

ORD record
ord-f99d460b32af4fb48f33566c553af2ec
Source dataset
uspto-grants-2014_06
Patent number
US08754054B2

Reaction notes

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