Cesium fluoride → HCID 67197146, compound

HRID 544913Notes

Reaction equation

HRID 544913 reaction equation
Br[C:2]1[S:6][C:5]([CH2:7][C:8]2[C:16]3[C:11](=[CH:12][CH:13]=[CH:14][C:15]=3[CH3:17])[N:10]([C@@H:18]3[O:35][C@H:34]([CH2:36][O:37][C:38](=[O:40])[CH3:39])[C@@H:29]([O:30][C:31](=[O:33])[CH3:32])[C@H:24]([O:25][C:26](=[O:28])[CH3:27])[C@H:19]3[O:20][C:21](=[O:23])[CH3:22])[CH:9]=2)=[CH:4][CH:3]=1.[S:41]1[CH:45]=[CH:44][CH:43]=[C:42]1B(O)O.[F-].[Cs+]>COCCOC.C(OCC)(=O)C.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[CH3:17][C:15]1[CH:14]=[CH:13][CH:12]=[C:11]2[C:16]=1[C:8]([CH2:7][C:5]1[S:6][C:2]([C:42]3[S:41][CH:45]=[CH:44][CH:43]=3)=[CH:3][CH:4]=1)=[CH:9][N:10]2[C@@H:18]1[O:35][C@H:34]([CH2:36][O:37][C:38](=[O:40])[CH3:39])[C@@H:29]([O:30][C:31](=[O:33])[CH3:32])[C@H:24]([O:25][C:26](=[O:28])[CH3:27])[C@H:19]1[O:20][C:21](=[O:23])[CH3:22]

Participants

7

Reactant 3

HCID 25953Cesium fluorideHCID 27339602-Thiopheneboronic acidHCID 67199228HCID 67199228, compound

Product 1

HCID 67197146HCID 67197146, compound

Reagents, catalysts & solvents 3

HCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 80711,2-DimethoxyethaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

A mixture of 3-(5-bromothiophen-2-yl-methyl)-4-methyl-1-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl)indole obtained in Example 45-(3) (190 mg), thiophene-2-boronic acid (229 mg), cesium fluoride (272 mg) and tetrakis(triphenylphosphine)-palladium(0) (34.5 mg) in 1,2-dimethoxyethane (6 ml) was refluxed for 6 hours under argon atmosphere. The reaction mixture was diluted with ethyl acetate and a saturated aqueous sodium hydrogen carbonate solution, and the organic layer was filtered through an aminosilane-treated silica gel pad. The filtrate was evaporated under reduced pressure to give crude 4-methyl-3-(5-(2-thienyl)-thiophen-2-yl-methyl)-1-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl)indole, which was partially deacetylated. This crude compound was dissolved in chloroform (6 ml), and thereto were added successively pyridine (0.121 ml), acetic anhydride (0.141 ml) and 4-(dimethylamino)pyridine (3.7 mg). After being stirred at room temperature for 4 hour, the solvent was evaporated under reduced pressure. The residue was dissolved in ethyl acetate (80 ml), and the mixture was washed with a 10% aqueous copper (II) sulfate solution (5 ml) twice and a saturated aqueous sodium hydrogen carbonate solution (5 ml), and dried over magnesium sulfate. The insoluble materials were filtered off, and the filtrate was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (hexane:ethyl acetate=90:10-50:50) to give 4-methyl-3-(5-(2-thienyl)thiophen-2-yl-methyl)-1-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl)indole (134 mg) as a yellow powder. APCI-Mass m/Z 657 (M+NH4).

Workup

  1. temperaturewas refluxed for 6 hours under argon atmosphere
  2. filtrationa saturated aqueous sodium hydrogen carbonate solution, and the organic layer was filtered through an aminosilane-
  3. additiontreated silica gel pad
  4. customThe filtrate was evaporated under reduced pressure

Sources & evidence

ORD record
ord-d1a84516b61b463a8cf85b674d97ca9f
Source dataset
uspto-grants-2011_05
Patent number
US07935674B2

Reaction notes

Loading…