Cesium fluoride → 1-(2,3,4,6-tetra-O-acetyl-beta-D-glucopyranosyl)-4-methyl-3-(5 (5-pyrimidinyl)-2-thienylmethyl)benzene

HRID 1625732Notes

Reaction equation

HRID 1625732 reaction equation
[C:1]([O:4][C@@H:5]1[C@@H:10]([O:11][C:12](=[O:14])[CH3:13])[C@H:9]([O:15][C:16](=[O:18])[CH3:17])[C@@H:8]([CH2:19][O:20][C:21](=[O:23])[CH3:22])[O:7][C@H:6]1[C:24]1[CH:29]=[CH:28][C:27]([CH3:30])=[C:26]([CH2:31][C:32]2[S:33][C:34](Cl)=[CH:35][CH:36]=2)[CH:25]=1)(=[O:3])[CH3:2].C([Sn](CCCC)(CCCC)[C:43]1[CH:44]=[N:45][CH:46]=[N:47][CH:48]=1)CCC.C(P(C(C)(C)C)C(C)(C)C)(C)(C)C.F[B-](F)(F)F.[H+].[F-].[Cs+]>O1CCOCC1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[C:1]([O:4][C@@H:5]1[C@@H:10]([O:11][C:12](=[O:14])[CH3:13])[C@H:9]([O:15][C:16](=[O:18])[CH3:17])[C@@H:8]([CH2:19][O:20][C:21](=[O:23])[CH3:22])[O:7][C@H:6]1[C:24]1[CH:29]=[CH:28][C:27]([CH3:30])=[C:26]([CH2:31][C:32]2[S:33][C:34]([C:43]3[CH:44]=[N:45][CH:46]=[N:47][CH:48]=3)=[CH:35][CH:36]=2)[CH:25]=1)(=[O:3])[CH3:2]

Participants

8

Reactant 5

HCID 25953Cesium fluorideHCID 28118Tetrafluoroboric acidHCID 83681Tris(1,1-dimethylethyl)phosphineHCID 27632495-(Tributylstannyl)pyrimidineHCID 666076841-(2,3,4,6-tetra-O-acetyl-beta-D-glucopyranosyl)-3-(5-chloro-2-thienylmethyl)-4-methylbenzene

Product 1

HCID 666072621-(2,3,4,6-tetra-O-acetyl-beta-D-glucopyranosyl)-4-methyl-3-(5 (5-pyrimidinyl)-2-thienylmethyl)benzeneYield 41.1%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
100 °C

Procedure

A mixed solution of 1-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl)-3-(5-chloro-2-thienylmethyl)-4-methylbenzene 57 (600 mg) obtained in Example 120-(1), tri-n-butyl(5-pyrimidinyl)tin (600 mg), tri-tert-butylphosphine.tetrafluoroboric acid adduct (116 mg), cesium fluoride (414 mg), and tris(dibenzylideneacetone)dipalladium (0) (91 mg) in 1,4-dioxane (18 ml) was heated under reflux at 100° C. for 3 hours under argon atmosphere. Insoluble materials were filtered off, and the filtrate was diluted with ethyl acetate and washed with brine. The solvent was evaporated under reduced pressure, and the residue was purified by silica gel column chromatography (hexane:ethyl acetate=75:25-40:60) to give 1-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl)-4-methyl-3-(5(5-pyrimidinyl)-2-thienylmethyl)benzene (266 mg) as colorless crystals. APCI-Mass m/Z 597 (M+H).

Workup

  1. filtrationInsoluble materials were filtered off
  2. additionthe filtrate was diluted with ethyl acetate
  3. washwashed with brine
  4. customThe solvent was evaporated under reduced pressure
  5. customthe residue was purified by silica gel column chromatography (hexane:ethyl acetate=75:25-40:60)

Sources & evidence

ORD record
ord-6a6667afe00a44fbb0fced49d54ec57e
Source dataset
uspto-grants-2014_07
Patent number
US08785403B2

Reaction notes

Loading…