Hydrochloric Acid → HCID 71455533, compound

HRID 1429758Notes

Reaction equation

HRID 1429758 reaction equation
[CH3:1][CH2:2][C:3]1[CH2:22][N:20]2[CH2:21][C@@H:5]([CH2:6][C@:7]([C:56]([O:58][CH3:59])=[O:57])([C:23]3[CH:24]=[C:25]4[C@:33]56[C@@H:37]7[C@:38]([CH2:53][CH3:54])([C@@H:42]([O:49][C:50]([CH3:52])=[O:51])[C@:43]([OH:48])([C:44]([O:46][CH3:47])=[O:45])[C@@H:32]5[N:31]([CH3:55])[C:26]4=[CH:27][C:28]=3[O:29][CH3:30])[CH:39]=[CH:40][CH2:41][N:36]7[CH2:35][CH2:34]6)[C:8]3[NH:16][C:15]4[CH:14]=[CH:13][C:12]([Cl:17])=[CH:11][C:10]=4[C:9]=3[CH2:18][CH2:19]2)[CH:4]=1.Cl.C(C[OH:66])(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:66])[CH2:22][N:20]2[CH2:21][C@@H:5]([CH2:6][C@:7]([C:56]([O:58][CH3:59])=[O:57])([C:23]3[CH:24]=[C:25]4[C@:33]56[C@@H:37]7[C@:38]([CH2:53][CH3:54])([C@@H:42]([O:49][C:50]([CH3:52])=[O:51])[C@:43]([OH:48])([C:44]([O:46][CH3:47])=[O:45])[C@@H:32]5[N:31]([CH3:55])[C:26]4=[CH:27][C:28]=3[O:29][CH3:30])[CH:39]=[CH:40][CH2:41][N:36]7[CH2:35][CH2:34]6)[C:8]3[NH:16][C:15]4[CH:14]=[CH:13][C:12]([Cl:17])=[CH:11][C:10]=4[C:9]=3[CH2:18][CH2:19]2)[CH2:4]1

Participants

10

Reactant 4

HCID 313Hydrochloric AcidHCID 64092,2,2-TrifluoroethanolHCID 4311764Sodium borohydrideHCID 71453801HCID 71453801, compound

Product 1

HCID 71455533HCID 71455533, compoundYield 42%

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 (52.6 mg, 0.109 mmol, 30 equiv) in H2O was cooled to 0° C. and air was bubbled through the mixture for 10 minutes. A solution of 10′-chloroanhydrovinblastine (18a, 3.0 mg, 0.0036 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 (2.7 mg, 0.073 mmol, 20 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:EtOAc=3:3:97) provided 10′-chlorovinblastine (18b, 1.3 mg, 0.0015 mmol, 42%) as a white solid and 10′-chloroleurosidine (0.8 mg, 0.00095 mmol, 26%).

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-89e8745b45e64932ac63da7cafb28491
Source dataset
uspto-grants-2015_01
Patent number
US08940754B2

Reaction notes

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