Triphenylphosphine → HCID 178419173, compound

HRID 2116512Notes

Reaction equation

HRID 2116512 reaction equation
[C:1]([O:4][C@@H:5]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]([CH2:20][O:21][C:22](=[O:24])[CH3:23])[S:8][CH:6]1[OH:7])(=[O:3])[CH3:2].[BH3:25].[CH2:26]([C:28]1[CH:41]=[CH:40][C:31]([CH2:32][C:33]2[CH:38]=[CH:37][NH+:36]=[CH:35][C:34]=2O)=[CH:30][CH:29]=1)[CH3:27].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OC(C)C)=O)=NC(OC(C)C)=O>O1CCCC1>[BH3:25].[CH2:26]([C:28]1[CH:41]=[CH:40][C:31]([CH2:32][C:33]2[CH:34]=[CH:35][NH+:36]=[CH:37][C:38]=2[O:7][C@@H:6]2[S:8][C@H:9]([CH2:20][O:21][C:22](=[O:24])[CH3:23])[C@@H:10]([O:16][C:17](=[O:19])[CH3:18])[C@H:11]([O:12][C:13](=[O:15])[CH3:14])[C@H:5]2[O:4][C:1](=[O:3])[CH3:2])=[CH:30][CH:29]=1)[CH3:27]

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 75555Diisopropyl diazene-1,2-dicarboxylateHCID 116462702,3,4,6-tetra-O-acetyl-5-thio-glucopyranoseHCID 178419172HCID 178419172, compound

Product 1

HCID 178419173HCID 178419173, compoundYield 86.9%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 2, 3, 4, 6-tetra-O-acetyl-5-thio-D-glucopyranose (481 mg, 1.32 mmol), 4-(4-ethylbenzyl)-3-hydroxypyridinium borane (200 mg, 0.881 mmol) and triphenylphosphine (230 mg, 1.32 mmol) in tetrahydrofuran (2.5 mL), diisopropyl azodicarboxylate (40% in toluene, 0.781 mL, 1.32 mmol) was added dropwise at 0° C. After stirring at room temperature for 2.5 hours, the reaction mixture was concentrated and the resulting residue was purified by silica gel column chromatography (hexane:ethyl acetate=2:1) to give a crude product of 4-(4-ethylbenzyl)-3-(2, 3, 4, 6-tetra-O-acetyl-5-thio-β-D-glucopyranosyloxy)pyridinium borane (440 mg) as a colorless oil. To this crude product, triethylamine:methanol:water (2:1:1, 3 mL) was added and the resulting mixture was stirred at room temperature for 24 hours. The reaction mixture was concentrated and the resulting residue was mixed, without purification, with methanol (1.8 mL) and 2M HCl (1.8 mL), followed by stirring at room temperature for 30 minutes. After addition of saturated sodium bicarbonate solution under ice cooling, the reaction mixture was extracted with chloroform (5 mL×4). The organic layers were concentrated and the resulting residue was purified by silica gel column chromatography (chloroform:methanol 7:1) to give the titled compound (30 mg, 9%).

Workup

  1. concentrationthe reaction mixture was concentrated
  2. customthe resulting residue was purified by silica gel column chromatography (hexane:ethyl acetate=2:1)

Sources & evidence

ORD record
ord-f97690900bba4585b0695c79e63473fd
Source dataset
uspto-grants-2008_10
Patent number
US07439232B2

Reaction notes

Loading…