Benzyl Bromide → HCID 67052771, compound

HRID 600145Notes

Reaction equation

HRID 600145 reaction equation
[C:1]([O:8][C@@H:9]1[C@@H:23]([OH:24])[C@@H:22]([OH:25])[C@@H:21]([CH3:26])[O:20][C@@H:10]1[O:11][C:12]1[CH:17]=[CH:16][C:15]([O:18][CH3:19])=[CH:14][CH:13]=1)(=[O:7])[CH2:2][CH2:3][C:4]([CH3:6])=[O:5].C([Sn](=O)CCCC)CCC.[CH2:37](Br)[C:38]1[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=1>C1(C)C=CC=CC=1.[I-].C([N+](CCCC)(CCCC)CCCC)CCC.O>[CH2:37]([O:24][C@H:23]1[C@@H:22]([OH:25])[C@@H:21]([CH3:26])[O:20][C@H:10]([O:11][C:12]2[CH:13]=[CH:14][C:15]([O:18][CH3:19])=[CH:16][CH:17]=2)[C@@H:9]1[O:8][C:1](=[O:7])[CH2:2][CH2:3][C:4]([CH3:6])=[O:5])[C:38]1[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=1

Participants

7

Reactant 3

HCID 7498Benzyl BromideHCID 61221Dibutyltin oxideHCID 67052741HCID 67052741, compound

Product 1

HCID 67052771HCID 67052771, compound

Reagents, catalysts & solvents 3

HCID 67553Tetrabutylammonium IodideCatalystHCID 962WaterSolventHCID 1140TolueneSolvent

Conditions

Temperature
60 °C

Procedure

4-Methoxyphenyl 2-O-levulinoyl-α-D-fucopyranoside (2.37 g, 6.46 mmol) and dibutyl tin oxide (1.61 g, 6.46 mmol) are dissolved in 70 mL of toluene. The mixture was refluxed with a Dean-Stark trap for 2.5 h. Then it was cooled to 60° C., benzylbromide and tetrabutylammonium iodide were added and refluxed for 2 h. After cooling to room temperature the reaction mixture was diluted with water and extracted 3 times with EtOAc, dried over Na2SO4 and concentrated. The crude product was purified by column chromatography (3:2 hexane/EtOAc) yielding 2.82 g (95%, 2 steps) of 6 as a colorless oil: [α]D: +140.8 (c=0.35, CHCl3). IR (thin film, CHCl3): 3015, 1739, 1713, 1503, 1362, 1050 cm−1. 1H NMR (CDCl3, 300 MHz) δ 1.29 (d, J=6.6 Hz, 3H), 2.14 (s, 3H), 2.62 (m, 3H), 2.72 (m, 2H), 3.76 (s, 3H), 3.92 (s, 1H), 4.09 (m, 2H), 4.74 (s, 2H), 5.28 (dd, J=10.2 Hz J=3.9 Hz, 1H), 5.50 (m, 1H), 6.82 (d, J=9.0 Hz, 2H), 6.98 (d, J=9.0 Hz, 2H), 7.33 (m, 5H). 13C NMR (CDCl3, 75 MHz) 16.2, 28.1, 29.9, 37.9, 55.7, 66.2, 69.8, 70.0, 72.4, 75.6, 96.2, 114.5, 118.0, 118.2, 127.6, 127.7, 127.9, 128.5, 137.7, 150.7, 155.0, 172.0, 206.0. MALDI-HRMS: m/z [M+Na]+ calcd 481.1833, obsd 481.1824.

Workup

  1. temperatureThe mixture was refluxed with a Dean-Stark trap for 2.5 h
  2. temperaturerefluxed for 2 h
  3. temperatureAfter cooling to room temperature the reaction mixture
  4. extractionextracted 3 times with EtOAc
  5. dry with materialdried over Na2SO4
  6. concentrationconcentrated
  7. customThe crude product was purified by column chromatography (3:2 hexane/EtOAc)

Sources & evidence

ORD record
ord-50fd9a12b3904cdf9b415ce5608155fe
Source dataset
uspto-grants-2011_03
Patent number
US07901687B2

Reaction notes

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