Imidazole → HCID 86718973, compound

HRID 1504987Notes

Reaction equation

HRID 1504987 reaction equation
[CH2:1]([O:8][C@@H:9]1[C@H:15]([OH:16])[C@H:14]([OH:17])[C@@H:13]([CH2:18][OH:19])[C:10]21[CH2:12][CH2:11]2)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.N1C=CN=C1.Cl[Si:26]([CH:39]([CH3:41])[CH3:40])([CH:36]([CH3:38])[CH3:37])[O:27][Si:28](Cl)([CH:32]([CH3:34])[CH3:33])[CH:29]([CH3:31])[CH3:30]>CN(C=O)C>[CH2:1]([O:8][C@H:9]1[C:10]2([CH2:12][CH2:11]2)[C@H:13]2[C@@H:14]([O:17][Si:26]([CH:36]([CH3:38])[CH3:37])([CH:39]([CH3:41])[CH3:40])[O:27][Si:28]([CH:32]([CH3:34])[CH3:33])([CH:29]([CH3:30])[CH3:31])[O:19][CH2:18]2)[C@H:15]1[OH:16])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

5

Reactant 3

HCID 795ImidazoleHCID 1724041,3-DichlorotetraisopropyldisiloxaneHCID 86718974HCID 86718974, compound

Product 1

HCID 86718973HCID 86718973, compoundYield 92.3%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a stirred mixture of triol 24 (2.9 g, 10.9 mmol) and imidazole (5.2 g, 76.8 mmol) in DMF (80 mL) at 0° C. under argon was added dropwise 1,3-dichloro-1,1,3,3-tetraisopropyldisiloxane (3.5 mL, 11.0 mmol). After the mixture was stirred at room temperature for 1 h, quenched with MeOH (15 mL) and water (100 mL) was added and the mixture was extracted with EtOAc (2×200 mL). The combined organic layers were washed with brine (40 mL) dried over Na2SO4. The solvent was removed and the residue was purified by silica gel column chromatography (EtOAc:Hexane 1:30 to 1:5) to give 25 (5.1 g, 92%) as an oil. [α]24D−105.94° (c 0.58, CHCl3); 1H NMR (500 MHz, CDCl3) δ 7.41-7.26 (m, 5H), 4.77 (d, J=12 Hz, 1H), 4.62 (d, J=12 Hz, 1H), 4.18-4.14 (m, 3H), 4.05 (dd, J=4.5, 12.0 Hz, 1H), 3.78 (dd, J=8, 12 Hz, 1H), 2.89 (m, 1H), 2.78 (d, J=2.0 Hz, 1H, OH) 1.08-0.97 (m, 28H), 0.61 (m, 1H), 0.43 (m, 1H), 0.32 (m, 1H), 0.24 (m, 1H); 13C NMR (125 MHz, CDCl3) δ 154.0, 147.3, 138.1, 128.4, 80.2, 74.2, 71.2, 71.1, 64.9, 50.1, 29.24 23.83, 17.6, 17.5, 17.4, 17.3, 17.2, 17.1, 17.0, 16.9, 16.8, 13.4, 12.9, 12.7, 12.5. 7.20; HR-MS Calcd. For (C27H46O5Si2+H)+ 507.2884. found 507.2798.

Workup

  1. customquenched with MeOH (15 mL) and water (100 mL)
  2. additionwas added
  3. extractionthe mixture was extracted with EtOAc (2×200 mL)
  4. washThe combined organic layers were washed with brine (40 mL)
  5. dry with materialdried over Na2SO4
  6. customThe solvent was removed
  7. customthe residue was purified by silica gel column chromatography (EtOAc:Hexane 1:30 to 1:5)

Sources & evidence

ORD record
ord-9bc7b6f0c28d4dfbadc10cf65f349d4c
Source dataset
uspto-grants-2015_12
Patent number
US09216960B2

Reaction notes

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