HCID 10623633, compound → HCID 10660917, compound

HRID 1636171Notes

Reaction equation

HRID 1636171 reaction equation
C[O-].[Na+].C([O:7][C@@H:8]1[C@@H:17]([O:18]C(=O)C)[C@H:16]([O:22]C(=O)C)[C@@H:15]([CH2:26][O:27]C(=O)C)[O:14][C@H:9]1[O:10][CH2:11][CH2:12][Br:13])(=O)C>CO>[O:10]([CH2:11][CH2:12][Br:13])[C@@H:9]1[O:14][C@H:15]([CH2:26][OH:27])[C@@H:16]([OH:22])[C@H:17]([OH:18])[C@H:8]1[OH:7]

Participants

4

Reactant 2

HCID 10623633HCID 10623633, compoundHCID 10942334Sodium Methoxide

Product 1

HCID 10660917HCID 10660917, compoundYield 93%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

A solution of NaOMe (0.1M, 0.3 mL) was added to a suspension of 4h (See FIG. 6) (300 mg, 0.66 mmol) in MeOH (3 mL) under N2 and stirred vigorously. After 4 hours, the resulting solution was passed through a Dowex 50W(H+) plug (2×1 cm, eluant MeOH) and the solvent removed to give 2-bromoethyl β-D-glucopyranoside 4c (See FIG. 6) (176 mg, 93%) as a white solid that was used directly in the next step. A sample was recrystallized from EtOH/EtOAc to give a colorless, crystalline solid; mp 74-78° C. (EtOH/EtOAc) [lit., (Helferich et al., Just. Lieb. Ann. Chem., 541:1-16 (1939), which is hereby incorporated by reference) mp 74-75° C. (EtOH/EtOAc)]; [α]26D=−22.4 (c 1.63, H2O) [lit., (Helferich et al., Just. Lieb. Ann. Chem., 541:1-16 (1939), which is hereby incorporated by reference) [α]19D=−26.1 (c 3.0, H2O)]; 1H NMR (400 MHz, CD3OD) δ 3.30 (t, J 8.4 Hz, 1H, H-2), 3.39-3.49 (m, 3H), 3.64-3.80 (m, 31H), 3.97 (br d, J6,6′ 11.7 Hz, 1H, H-6′), 4.02 (dt, Jt 6.5 Hz, Jd 11.3 Hz, 1H, —OCHH′—), 4.23 (dt, Jt 6.5 Hz, Jd 11.3 Hz, 1H, —OCHH′—), 4.44 (d, J1,2 7.9 Hz, 1H, H-1). NaSSO2CH3 (100 mg, 0.75 mmol) was added to a solution of 4c (See FIG. 6) (176 mg, 0.61 mmol) in DMF (7 mL) under N2 and warmed to 50° C. After 15 hours, the solution was cooled and the solvent removed. The residue was purified by flash chromatography (MeOH:EtOAc, 1:9) to give 1c (See FIG. 6) (144 mg, 74%) as a hygroscopic foam; [α]27D=−15.8 (c 0.88, H2O); IR(KBr) 3400 cm−1 (OH), 1310, 1131 cm−1 (S—SO2); 1H NMR (500 MHz, D2O, COSY) δ 3.07 (dd, J1,2 8.1 Hz, J2,3 9.4 Hz, 1H, H-2), 3.16 (dd, J3 4 9.0 Hz J4,5 9.8Hz, 1H, H-4), 3.24 (ddd, J4,5 9.8 Hz, J5,6 6.0 Hz, J5,6′ 2.3Hz, 1H, H-5), 3.27 (t, J 9.0 Hz, 1H, H-3), 3.30-3.33 (m, 2H, —CH2S—), 3.34 (s, 3H, CH3SO2—), 3.50 (dd, J5,6 6.0 Hz, J6,6′ 12.4 Hz, 1H, H-6), 3.69 (dd, J5,6 2.3 Hz, J6,6′ 12.4 Hz, 1H, H-6′), 3.81 (dt, Jt 5.8 Hz, Jd 11.5 Hz, 1H, —OCHH′—), 4.00 (dt, Jt 5.7 Hz, Jd 11.4 Hz, 1H, —OCHH′—), 4.30 (d, J1,2 8.1 Hz, 1H, H-1); 13C NMR (50 MHz, D2O) δ 36.9 (—CH2S—), 51.0 (CH3SO2—), 62.0 (—OCH2—), 69.5, 70.9, 74.3, 76.7, 77.3 (C-2, C-3, C-4, C-5, C-6), 103.7 (C-1); HRMS m/z (FAB+): Found 341.0351 (M+Na+); C9H18O8S2Na requires 341.0341.

Workup

  1. customthe solvent removed

Sources & evidence

ORD record
ord-ee1385bff227424eb9cb5986a33c11e4
Source dataset
uspto-grants-2003_01
Patent number
US06512098B2

Reaction notes

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