Boron trifluoride etherate → HCID 10623633, compound

HRID 1636170Notes

Reaction equation

HRID 1636170 reaction equation
B(F)(F)F.CCOCC.[C:10]([O:13][CH:14]1[O:31][C@H:30]([CH2:32][O:33][C:34](=[O:36])[CH3:35])[C@@H:25]([O:26][C:27](=[O:29])[CH3:28])[C@H:20]([O:21][C:22](=[O:24])[CH3:23])[C@H:15]1[O:16][C:17](=[O:19])[CH3:18])(=O)[CH3:11].[Br:37]CCO>C(Cl)Cl>[C:17]([O:16][C@@H:15]1[C@@H:20]([O:21][C:22](=[O:24])[CH3:23])[C@H:25]([O:26][C:27](=[O:29])[CH3:28])[C@@H:30]([CH2:32][O:33][C:34](=[O:36])[CH3:35])[O:31][C@H:14]1[O:13][CH2:10][CH2:11][Br:37])(=[O:19])[CH3:18]

Participants

5

Reactant 3

HCID 8000Boron trifluoride etherateHCID 108982-BromoethanolHCID 10293747D-Glucopyranose, pentaacetate

Product 1

HCID 10623633HCID 10623633, compoundYield 61.2%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

BF3.Et2O (3.3 mL, 26.0 mmol) was added dropwise over the course of 15 minutes to a solution of 1,2,3,4,6-penta-O-acetyl-α,β-D-glucose (2 g, 5.1 mmol) and Br(CH2)2OH (0.45 mL, 6.3 mmol) in CH2Cl2 (9 mL) at 0° C. under N2. After 1.5 hours, the solution was warmed to room temperature. After 20 hours the reaction solution was added to ice water (15 mL) and extracted with CH2Cl2 (15 mL×3). These extracts were combined, washed with water (15 mL), sat. NaHCO3 (aq., 15 mL), water (15 mL), dried (MgSO4), filtered, and the solvent removed. The residue was purified by flash chromatography (EtOAc:hexane, 1:3) to give 2-bromoethyl 2,3,4,6-tetra-O-acetyl-β-D-glucopyranoside (4h) (See FIG. 6) (1.42 g, 61%) as a white solid; mp 118-120° C. (EtOAc/iso-octane) [lit., (Coles et al., J. Am. Chem. Soc., 60:1020-1022 (1938), which is hereby incorporated by reference) mp 117.3° C. (EtOH)]; [α]27D=−11.9 (c 1.65, CHCl3) [lit., (Helferich et al., Just. Lieb. Ann. Chem., 541:1-16 (1939), which is hereby incorporated by reference) [α]20D=−12.3 (c 0.2, CHCl3)]; 1H NMR (200 MHz, CDCl3) δ 2.00, 2.02, 2.07, 2.09 (s×4, 3H×4, Ac×4), 3.42-3.51 (m, 2H), 3.67-3.87 (m, 2H), 4.10-4.31 (m, 3H), 4.57 (d, J1,2 8 Hz, 1H, H-1), 4.97-5.27 (m, 3H). NaSSO2CH3 (260 mg, 1.94 mmol) was added to a solution of 4h (See FIG. 6) (640 mg, 1.41 mmol) in DMF (18 mL) under N2 and warmed to 50° C. After 25 hours, the solution was cooled and the solvent removed. The residue was purified by flash chromatography (EtOAc:hexane, 1:1) and the resulting solid recrystallized from EtOAc/hexane to give 1h (See FIG. 6) (544 mg, 80%) as a white solid; mp 115-116° C. (EtOAc/hexane); [α]27D=+5.4 (c 1.06, CHCl3); IR (KBr) 1758, 1741 cm−1 (C═O), 1314, 1133 cm−1 (S—SO,); 1H NMR (500 MHz, CDCl3, COSY) δ 1.99, 2.02, 2.06, 2.08 (s×4, 3H×4, Ac×4), 3.30-3.38 (m, 2H, —CH2S—), 3.34 (s, 3H, CH3SO2—), 3.70 (ddd, J4,5 9.9 Hz, J5,6 2.2 Hz, J5,6′ 4.6 Hz, 1H. H-5), 3.83 (ddd, J 5.6 Hz, J 7.4 Hz, J 10.5 Hz, 1H, —OCHH′—), 4.13-4.18 (m, 2H, H-6, —OCHH′—), 4.24 (dd, J5 6′ 4.6 Hz, J6,6′ 12.4 Hz, 1H, H-6′), 4.55 (d, J1,2 8.1 Hz, 1H, H-1), 4.98 (dd,J1,2 8.1 Hz, J2,3 9.7 Hz, 1H, H-2), 5.07 (t, J 9.9 Hz, 1 H, H-4), 5.19 (t, J 9.6 Hz, 1H, H-3); 13C NMR (125 MHz, CDCl3, DEPT) δ 20.5, 20.7 (q×2, CH3COO—×4), 36.0, (t, —CH2S—), 50.6 (q, CH3SO2—), 61.6 (t, —OCH2—), 68.1, 70.8, 71.9, 72.5 (d×4, C-2, C-3, C-4, C-5), 68.4 (t, C-6), 100.8 (d, C-1), 169.3, 170.0, 170.5 (s×3 CH3COO—×4); HRMS m/z (FAB+): Found 487.0940 (M÷H+); C17H27O12S2 requires 487.0944.

Workup

  1. extractionextracted with CH2Cl2 (15 mL×3)
  2. washwashed with water (15 mL), sat. NaHCO3 (aq., 15 mL), water (15 mL)
  3. dry with materialdried (MgSO4)
  4. filtrationfiltered
  5. customthe solvent removed
  6. customThe residue was purified by flash chromatography (EtOAc:hexane, 1:3)

Sources & evidence

ORD record
ord-a3267f5599dd48a1b847f2365cd8d88e
Source dataset
uspto-grants-2003_01
Patent number
US06512098B2

Reaction notes

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