Sodium Chloride → 1-deoxy-1-{4-[2(trimethylsilyl)ethoxymethoxy]phenylthio}-2,3,4,6-tetra-O-acetyl-beta-D-galactopyranose

HRID 1637439Notes

Reaction equation

HRID 1637439 reaction equation
[OH:1][C:2]1[CH:7]=[CH:6][C:5]([S:8][C@@H:9]2[O:26][C@H:25]([CH2:27][O:28][C:29](=[O:31])[CH3:30])[C@H:20]([O:21][C:22](=[O:24])[CH3:23])[C@H:15]([O:16][C:17](=[O:19])[CH3:18])[C@H:10]2[O:11][C:12](=[O:14])[CH3:13])=[CH:4][CH:3]=1.C(N(CC)C(C)C)(C)C.[CH3:41][Si:42]([CH3:49])([CH3:48])[CH2:43][CH2:44][O:45][CH2:46]Cl.[Na+].[Cl-]>C(Cl)Cl>[CH3:41][Si:42]([CH3:49])([CH3:48])[CH2:43][CH2:44][O:45][CH2:46][O:1][C:2]1[CH:3]=[CH:4][C:5]([S:8][C@@H:9]2[O:26][C@H:25]([CH2:27][O:28][C:29](=[O:31])[CH3:30])[C@H:20]([O:21][C:22](=[O:24])[CH3:23])[C@H:15]([O:16][C:17](=[O:19])[CH3:18])[C@H:10]2[O:11][C:12](=[O:14])[CH3:13])=[CH:6][CH:7]=1

Participants

6

Reactant 4

HCID 5234Sodium ChlorideHCID 81531DiisopropylethylamineHCID 27242712-Chloromethyl 2-(trimethylsilyl)ethyl etherHCID 702546491-deoxy-1-(4-hydroxyphenylthio)-2,3,4,6-tetra-O-acetyl-beta-D-galactopyranose

Product 1

HCID 219675931-deoxy-1-{4-[2(trimethylsilyl)ethoxymethoxy]phenylthio}-2,3,4,6-tetra-O-acetyl-beta-D-galactopyranoseYield 89%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of thioglycoside 78 (1.40 g, 3.10 mmol) in 15 mL of methylene chloride is added N,N-diisopropylethylamine (0.64 mL, 3.70 mmol), followed by 2-(trimethylsilyl)ethoxymethyl chloride (0.60 mL, 3.40 mmol). The mixture is stirred at room temperature for 2 h, poured into saturated NaCl (50 mL) and extracted with CH2Cl2 (2×50 mL), dried over Na2SO4, concentrated, and purified by flash chromatography (40% EtOAc/hexane) to give 1.60 g (89%) of 1-deoxy-1-{4-[2(trimethylsilyl)ethoxymethoxy]phenylthio}-2,3,4,6-tetra-O-acetyl-β-D-galactopyranose 79 as a colorless oil: Rf 0.4 (33% EtOAc/hexane); 1H NMR (CDCl3, 270 MHz) δ 7.46 (d, J=8.4 Hz, 2H), 6.98 (d, J=8.4 Hz, 2H), 5.40 (d, J=3.3 Hz, 1H, H-4), 5.22 (s, 2H, SEM), 5.20 (dd, J=9.9, 9.9 Hz, 1H, H-2), 5.02 (dd, J=3.3, 9.9 Hz, 1H, H-3), 4.58 (d, J=9.9 Hz, 1H, H-1), 4.18 (dd, J=6.6, 11.2 Hz, 1H), 4.10 (dd, J=6.6, 11.2 Hz, 1H), 3.89 (dd, J=6.6, 6.6 Hz, 1H, H-5), 3.75 (t, J=8.4 Hz, 2H, SEM), 2.11 (s, 3H, OAc), 2.10 (s, 3H, OAc), 2.04 (s, 3H, OAc), 1.98 (s, 3H, OAc), 0.94 (t, J=8.4 Hz, 2H, CH2 --TMS), 0.01 (s, 9H, SiMe3).

Workup

  1. extractionextracted with CH2Cl2 (2×50 mL)
  2. dry with materialdried over Na2SO4
  3. concentrationconcentrated
  4. custompurified by flash chromatography (40% EtOAc/hexane)

Sources & evidence

ORD record
ord-49e9aa3c528b4e24acff24806dd3c802
Source dataset
uspto-grants-2000_03
Patent number
US06040433

Reaction notes

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