Water → [(2R,3R,4S,5R,6R)-3,4,5-triacetoxy-6-[3-(4-hydroxybenzoyl)-4-methyl-indol-1-yl]tetrahydropyran-2-yl]methyl acetate

HRID 2284861Notes

Reaction equation

HRID 2284861 reaction equation
[C:1]([O:4][CH2:5][C@@H:6]1[C@@H:11]([O:12][C:13](=[O:15])[CH3:14])[C@H:10]([O:16][C:17](=[O:19])[CH3:18])[C@@H:9]([O:20][C:21](=[O:23])[CH3:22])[C@H:8]([N:24]2[C:32]3[C:27](=[C:28]([CH3:33])[CH:29]=[CH:30][CH:31]=3)[CH:26]=[CH:25]2)[O:7]1)(=[O:3])[CH3:2].ClCCl.Br[C:38]1[CH:46]=[CH:45][C:41]([C:42](Cl)=[O:43])=[CH:40][CH:39]=1.[Cl-].[Cl-].[Cl-].[Al+3].[OH2:51]>C(Cl)(Cl)Cl>[C:1]([O:4][CH2:5][C@@H:6]1[C@@H:11]([O:12][C:13](=[O:15])[CH3:14])[C@H:10]([O:16][C:17](=[O:19])[CH3:18])[C@@H:9]([O:20][C:21](=[O:23])[CH3:22])[C@H:8]([N:24]2[C:32]3[C:27](=[C:28]([CH3:33])[CH:29]=[CH:30][CH:31]=3)[C:26]([C:42](=[O:43])[C:41]3[CH:45]=[CH:46][C:38]([OH:51])=[CH:39][CH:40]=3)=[CH:25]2)[O:7]1)(=[O:3])[CH3:2]

Participants

7

Reactant 5

HCID 962WaterHCID 6344DichloromethaneHCID 685154-Bromobenzoyl chlorideHCID 6451240Aluminum(III) ChlorideHCID 671958784-methyl-1-(2,3,4,6-tetra-O-acetyl-beta-D-glucopyranosyl)indole

Product 1

HCID 118045277[(2R,3R,4S,5R,6R)-3,4,5-triacetoxy-6-[3-(4-hydroxybenzoyl)-4-methyl-indol-1-yl]tetrahydropyran-2-yl]methyl acetateYield 46.09%

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Procedure

To a 0.5 L stirred round bottom, purged with nitrogen, charge in order: [(2R,3R,4S,5R,6R)-3,4,5-triacetoxy-6-(4-methylindol-1-yl)tetrahydropyran-2-yl]methyl acetate (29.5 mmol), dichloromethane (100 mL), and 4-bromobenzoyl chloride (30.9 mmol). Cool the mixture in an icebath and add aluminum trichloride (88.4 mmol). After stirring, with cooling, for 1.5 hours, pour the reaction mixture over ice and dilute with water (100 mL) and chloroform (100 mL). Separate the organic phase and wash the aqueous with chloroform (100 mL). Combine the organics and wash with concentrated sodium bicarbonate solution (200 mL) and brine (200 mL). Dry over sodium sulphate, filter, and concentrate. Purify by flash chromatography over silica gel (330 g) eluting with 5-25% EtOAc/chloroform to give the title compound (7.9 g; 46.09% yield): mass spectrum (m/z): 582.4 (M+1), 580.4 (M−H).

Workup

  1. custompurged with nitrogen
  2. additioncharge in order
  3. temperatureCool the mixture in an icebath
  4. stirringAfter stirring
  5. temperaturewith cooling, for 1.5 hours
  6. additionpour the reaction mixture over ice
  7. customSeparate the organic phase
  8. washwash the aqueous with chloroform (100 mL)
  9. washCombine the organics and wash with concentrated sodium bicarbonate solution (200 mL) and brine (200 mL)
  10. dry with materialDry over sodium sulphate
  11. filtrationfilter
  12. concentrationconcentrate
  13. customPurify by flash chromatography over silica gel (330 g)
  14. washeluting with 5-25% EtOAc/chloroform

Sources & evidence

ORD record
ord-3624aab4611b4749839f67d885e4903b
Source dataset
uspto-grants-2015_09
Patent number
US09145437B2

Reaction notes

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