Imidazole → HCID 69965447, compound

HRID 1745927Notes

Reaction equation

HRID 1745927 reaction equation
[C:1]1(=[O:37])[N:5]([C@@H:6]2[C@@H:19]([O:20][C:21](=[O:28])[C:22]3[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=3)[C@H:18]([OH:29])[C@@H:17]([CH2:30][OH:31])[O:16][C@H:7]2[S:8][C:9]2[CH:14]=[CH:13][C:12]([CH3:15])=[CH:11][CH:10]=2)[C:4](=[O:32])[C:3]2=[CH:33][CH:34]=[CH:35][CH:36]=[C:2]12.[C:38]([Si:42](Cl)([C:49]1[CH:54]=[CH:53][CH:52]=[CH:51][CH:50]=1)[C:43]1[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=1)([CH3:41])([CH3:40])[CH3:39].N1C=CN=C1>CN(C=O)C.CCOC(C)=O>[C:4]1(=[O:32])[N:5]([C@@H:6]2[C@@H:19]([O:20][C:21](=[O:28])[C:22]3[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=3)[C@H:18]([OH:29])[C@@H:17]([CH2:30][O:31][Si:42]([C:38]([CH3:41])([CH3:40])[CH3:39])([C:49]3[CH:50]=[CH:51][CH:52]=[CH:53][CH:54]=3)[C:43]3[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=3)[O:16][C@H:7]2[S:8][C:9]2[CH:14]=[CH:13][C:12]([CH3:15])=[CH:11][CH:10]=2)[C:1](=[O:37])[C:2]2=[CH:36][CH:35]=[CH:34][CH:33]=[C:3]12

Participants

6

Reactant 3

HCID 795ImidazoleHCID 94078tert-ButyldiphenylchlorosilaneHCID 69599737HCID 69599737, compound

Product 1

HCID 69965447HCID 69965447, compoundYield 80.2%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Procedure

A mixture of p-methylphenyl 2-deoxy-2-phthalimido-3-O-benzoyl-1-thio-β-D-glucopyranoside (70.0 mg, 0.1349 mmol), tert-butylchlorodiphenylsilane (83.2 mg, 0.2968 mmol), and imidazole (27.8 mg, 0.4047 mmol) in DMF (4 mL) was stirred for 4 h. The mixture was diluted with EtOAc (35 mL) and washed with water (3×10 mL). The organic layer was dried over Na2SO4 and concentrated. The residue was purified by column chromatography on silica gel (hexanes/EtOAc 4:1 to 3:1) to give product (82.0 mg, 80%) as a thick oil: 1H NMR (500 MHz, CDCl3) δ 7.85 (dd, J=83, 1.1 Hz, 2H), 7.80 (d, J=6.4 Hz, 1H), 7.73–7.77 (m, 5H), 7.60–7.66 (m, 2H), 7.28–7.47 (m, 11H), 7.00 (d, J=8.1 Hz, 2H), 5.93 (dd, J=10.3, 8.9 Hz, 1H), 5.77 (d, J=10.4 Hz, 1H), 4.47 (t, J=10.3 Hz, 1H), 4.01–4.09 (m, 2H), 3.97 (t, J=9.3 Hz, 1H), 3.78 (dt, J=9.6, 4.3 Hz, 1H), 3.18 (br. s, 1H), 2.28 (s, 3H), 1.09 (s, 9H); 13C NMR (125 MHz, CDCl3) δ 167.88, 167.17, 166.84, 138.14, 135.65, 135.60, 134.17, 134.04, 133.30, 133.26, 132.95, 132.91, 131.55, 131.21, 129.84, 129.77, 129.61, 128.90, 128.30, 127.79, 127.76, 123.54, 123.50, 83.29, 79.76, 75.38, 71.05, 64.12, 53.54, 26.80, 21.10, 19.22; HRMS (M+Na) calcd for C44H43O7NSSiNa 780.2427, found 780.2460 washed with H2O (15 mL), sat. NaHCO3 (15 mL), and brine (10 mL). The organic layer was dried (Na2SO4) and concentrated. The residue was subjected to column chromatography (hexanes/EtOAc 3:1) to give product (280 mg, 96%) as a foam: 1H NMR (500 MHz, CDCl3) δ 7.86 (dd, J=8.4, 1.0 Hz, 2H), 7.82 (d, J=6.4 Hz, 1H), 7.75 (d, J=6.3 Hz, 1H), 7.65–7.69 (m, 2H), 7.48 (t, J=75 Hz, 1H), 7.28–7.37 (m, 9H), 7.03 (d, J=7.7 Hz, 2H), 5.90 (dd, J=10.2, 8.8 Hz, 1H), 5.73 (d, J=10.4 Hz, 1H), 4.58–4.65 (ABq, J=11.9 Hz, 2H), 4.48 (t, J=10.4 Hz, 1H), 3.81–3.95 (m, 4H), 3.15 (d, J=3.7 Hz, 1H), 2.29 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 167.86, 167.20, 166.86, 138.38, 137.86, 134.22, 134.11, 133.49, 133.38, 131.59, 131.27, 129.88, 129.66, 128.90, 128.43, 128.37, 127.77, 127.72, 123.58, 83.47, 78.71, 75.27, 73.72, 71.41, 70.10, 53.54, 21.14; HRMS (M+Na) calcd for C35H31O7NSNa 632.1719. found 632.1747.

Workup

  1. washwashed with water (3×10 mL)
  2. dry with materialThe organic layer was dried over Na2SO4
  3. concentrationconcentrated
  4. customThe residue was purified by column chromatography on silica gel (hexanes/EtOAc 4:1 to 3:1)

Sources & evidence

ORD record
ord-07f524f138b843a0b50d573163897b48
Source dataset
uspto-grants-2006_03
Patent number
US07019131B2

Reaction notes

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