Imidazole → HCID 58747916, compound

HRID 1942572Notes

Reaction equation

HRID 1942572 reaction equation
[CH2:1]([O:8][C@@H:9]([C@H:12]([C@@H:21]([CH2:23][O:24][CH2:25][C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1)[OH:22])[O:13][CH2:14][C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1)[CH2:10][OH:11])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.N1C=CN=C1.[CH3:37][C:38]([Si:41](Cl)([CH3:43])[CH3:42])([CH3:40])[CH3:39]>CN(C=O)C>[CH2:1]([O:8][C@@H:9]([C@H:12]([C@@H:21]([CH2:23][O:24][CH2:25][C:26]1[CH:27]=[CH:28][CH:29]=[CH:30][CH:31]=1)[OH:22])[O:13][CH2:14][C:15]1[CH:16]=[CH:17][CH:18]=[CH:19][CH:20]=1)[CH2:10][O:11][Si:41]([C:38]([CH3:40])([CH3:39])[CH3:37])([CH3:43])[CH3:42])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

5

Reactant 3

HCID 795ImidazoleHCID 28928tert-Butyldimethylsilyl chlorideHCID 58747826HCID 58747826, compound

Product 1

HCID 58747916HCID 58747916, compoundYield 93%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
0 °C

Procedure

A mixture of 239 (5.24 g, 12.4 mmol), imidazole (3.72 g, 54.6 mmol), and TBDMSCl (2.07 g, 13.6 mmol) in dry DMF (50 mL) was stirred at 0° C. under N2 for 30 min. The reaction was quenched with ice (20 mL), and the reaction mixture was partitioned between Et2O (200 mL) and H2O (100 mL). The separated organic phase was washed with H2O (100 mL) and brine (100 mL). The organic layer was dried over anhydrous Na2SO4 and concentrated. The residue was purified by flash chromatography (hexanes:EtOAc, 3:1) to give a colorless oil 240 (6.164 g, 93%): [α]D −140.4° (c 0.87, CHCl3); 1H NMR (CDCl3) δ 7.35-7.25 (15H, m, Ar), 4.74 and 4.60 (2H, 2d, Ja,b=11.7 Hz, CH2Ph), 4.69 and 4.51 (2H, 2d, Ja,b=11.9 Hz, CH2Ph), 4.51 and 4.45 (2H, 2d, Ja,b=11.6 Hz, CH2Ph), 4.05 (1H, dddd, J3,4=2.3 Hz, J4,5a=J4,5b=5.9 H,J4,OH=5.9 Hz, H-4), 3.88 (1H, dd, J1a,1b=11.0 Hz, J1a,2=4.2 Hz, H-1a), 3.78 (1H, dd, J1b,2=4.9 Hz, H-1b), 3.77 (1H, dd, J2,3=4.1 Hz, H-3), 3.73 (1H, ddd, H-2), 3.54(1H, dd, H-5a), 3.49 (1H, dd, H-5b), 3.02 (1H, d, OH), 0.891 (9H, s, (CH3)3CSi), 0.05 (6H, s, (CH3)2Si); 13C NMR (CDCl3) δ 149.11, 145.62, 140.95 (3Cipso), 128.35-127.60 (15C, Ar), 80.25 (C-2), 77.25 (C-3), 73.65, 73.26, 72.84 (3CH2Ph), 71.16 (C-5), 69.75 (C-4), 62.04 (C-1), 25.88 (3C, (CH3)3CSi) 18.23 (1C, CSi), −5.40, −5.44 (2C, (CH3)2Si); MALDI-TOF MS: m/e 537.89 (M++H), 559.33 (M++Na). Anal. Calcd for C32H44O5Si: C, 71.60; H, 8.26. Found: C, 71.44; H, 8.34.

Workup

  1. customThe reaction was quenched with ice (20 mL)
  2. customthe reaction mixture was partitioned between Et2O (200 mL) and H2O (100 mL)
  3. washThe separated organic phase was washed with H2O (100 mL) and brine (100 mL)
  4. dry with materialThe organic layer was dried over anhydrous Na2SO4
  5. concentrationconcentrated
  6. customThe residue was purified by flash chromatography (hexanes:EtOAc, 3:1)

Sources & evidence

ORD record
ord-9b24d2181d3b43a6ad5ca06ec10f7363
Source dataset
uspto-grants-2013_03
Patent number
US08389565B2

Reaction notes

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