Hydrochloric Acid → HCID 71459160, compound

HRID 1429762Notes

Reaction equation

HRID 1429762 reaction equation
[CH3:1][CH2:2][C:3]1[CH2:23][N:21]2[CH2:22][C@@H:5]([CH2:6][C@:7]([C:57]([O:59][CH3:60])=[O:58])([C:24]3[CH:25]=[C:26]4[C@:34]56[C@@H:38]7[C@:39]([CH2:54][CH3:55])([C@@H:43]([O:50][C:51]([CH3:53])=[O:52])[C@:44]([OH:49])([C:45]([O:47][CH3:48])=[O:46])[C@@H:33]5[N:32]([CH3:56])[C:27]4=[CH:28][C:29]=3[O:30][CH3:31])[CH:40]=[CH:41][CH2:42][N:37]7[CH2:36][CH2:35]6)[C:8]3[NH:16][C:15]4[CH:14]=[CH:13][C:12]([O:17][CH3:18])=[CH:11][C:10]=4[C:9]=3[CH2:19][CH2:20]2)[CH:4]=1.Cl.C(C[OH:67])(F)(F)F.[BH4-].[Na+]>O.O.O.O.O.O.O.C([O-])(=O)C([O-])=O.[Fe+3].C([O-])(=O)C([O-])=O.C([O-])(=O)C([O-])=O.[Fe+3].CCOC(C)=O.CO.CCN(CC)CC>[CH3:1][CH2:2][C@@:3]1([OH:67])[CH2:23][N:21]2[CH2:22][C@@H:5]([CH2:6][C@:7]([C:57]([O:59][CH3:60])=[O:58])([C:24]3[CH:25]=[C:26]4[C@:34]56[C@@H:38]7[C@:39]([CH2:54][CH3:55])([C@@H:43]([O:50][C:51]([CH3:53])=[O:52])[C@:44]([OH:49])([C:45]([O:47][CH3:48])=[O:46])[C@@H:33]5[N:32]([CH3:56])[C:27]4=[CH:28][C:29]=3[O:30][CH3:31])[CH:40]=[CH:41][CH2:42][N:37]7[CH2:36][CH2:35]6)[C:8]3[NH:16][C:15]4[CH:14]=[CH:13][C:12]([O:17][CH3:18])=[CH:11][C:10]=4[C:9]=3[CH2:19][CH2:20]2)[CH2:4]1

Participants

10

Reactant 4

HCID 313Hydrochloric AcidHCID 64092,2,2-TrifluoroethanolHCID 4311764Sodium borohydrideHCID 71450167HCID 71450167, compound

Product 1

HCID 71459160HCID 71459160, compoundYield 48%

Reagents, catalysts & solvents 5

HCID 57370413Iron(3+) ethanedioate--water (2/3/6)CatalystHCID 887MethanolSolventHCID 962WaterSolvent3×HCID 8471TriethylamineSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

A mixture of iron(III) oxalate hexahydrate (79.4 mg, 0.13 mmol, 30 equiv) in H2O (22 mL) was cooled to 0° C. and air was bubbled through the mixture for 10 minutes. A solution of 10′-methoxyanhydro-vinblastine (22a, 4.5 mg, 0.0055 mmol, 1 equiv) in H2O (0.5 mL), aqueous 0.1 N HCl (0.5 mL), and CF3CH2OH (0.1 mL) was transferred by pipette to the mixture and NaBH4 (4.1 mg, 0.11 mmol, 20 equiv) in H2O (1 mL) was added to the mixture at 0° C. The resulting mixture was stirred for 30 min before being quenched by addition of 28-30% aqueous NH4OH (10 mL). The mixture was extracted with 10% MeOH in CH2Cl2 and the organic layer was dried over Na2SO4 and concentrated under reduced pressure. PTLC (SiO2, Et3N:MeOH:EtOAc=3:3:97) provided 10′-methoxyvinblastine (22b, 2.2 mg, 0.0026 mmol, 48%) as a white solid and 10′-methoxyleurosidine (1.3 mg, 0.0015 mmol, 28%).

Workup

  1. customair was bubbled through the mixture for 10 minutes
  2. additionwas added to the mixture at 0° C
  3. custombefore being quenched by addition of 28-30% aqueous NH4OH (10 mL)
  4. extractionThe mixture was extracted with 10% MeOH in CH2Cl2
  5. dry with materialthe organic layer was dried over Na2SO4
  6. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-67c1e353b31b4c1c81858fa06e0f5daf
Source dataset
uspto-grants-2015_01
Patent number
US08940754B2

Reaction notes

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