Hydrochloric Acid → HCID 53232570, compound

HRID 1429760Notes

Reaction equation

HRID 1429760 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]([S: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].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]([S:17][CH3:18])=[CH:11][C:10]=4[C:9]=3[CH2:19][CH2:20]2)[CH2:4]1

Participants

9

Reactant 4

HCID 313Hydrochloric AcidHCID 64092,2,2-TrifluoroethanolHCID 4311764Sodium borohydrideHCID 71462687HCID 71462687, compound

Product 1

HCID 53232570HCID 53232570, compoundYield 31%

Reagents, catalysts & solvents 4

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

Conditions

Temperature
0 °C

Procedure

A mixture of iron(III) oxalate hexahydrate (280.3 mg, 0.58 mmol, 30 equiv) in H2O (77 mL) was cooled to 0° C. and air was bubbled through the mixture for 10 minutes. A solution of 10′-thiomethylanhydro-vinblastine (20a, 16.2 mg, 0.019 mmol) 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 (14.6 mg, 0.39 mmol, 1 equiv) in H2O (1 mL) was added to the mixture at 0° C. The resulting mixture was stirred for 30 minutes 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:FtOAc=3:3:97) provided 10′-thiomethylvinblastine (20b, 5.1 mg, 0.0060 mmol, 31%) as a white solid and 10′-thiomethylleurosidine (2.5 mg, 0.0029 mmol, 15%).

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-8299c8f838944580a49b4f50606ea79d
Source dataset
uspto-grants-2015_01
Patent number
US08940754B2

Reaction notes

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