Imidazole → diisopropyl (E)-3-acetoxymethyl-4-t-butyldiphenylsilyloxybut-1-enylphosphonate

HRID 1708086Notes

Reaction equation

HRID 1708086 reaction equation
[C:1]([O:4][CH2:5][CH:6]([CH2:19][OH:20])/[CH:7]=[CH:8]/[P:9](=[O:18])([O:14][CH:15]([CH3:17])[CH3:16])[O:10][CH:11]([CH3:13])[CH3:12])(=[O:3])[CH3:2].N1C=CN=C1.[Si:26](Cl)([C:39]([CH3:42])([CH3:41])[CH3:40])([C:33]1[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1)[C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1>C1COCC1>[C:1]([O:4][CH2:5][CH:6]([CH2:19][O:20][Si:26]([C:39]([CH3:42])([CH3:41])[CH3:40])([C:33]1[CH:34]=[CH:35][CH:36]=[CH:37][CH:38]=1)[C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1)/[CH:7]=[CH:8]/[P:9](=[O:18])([O:14][CH:15]([CH3:16])[CH3:17])[O:10][CH:11]([CH3:13])[CH3:12])(=[O:3])[CH3:2]

Participants

5

Reactant 3

HCID 795ImidazoleHCID 94078tert-ButyldiphenylchlorosilaneHCID 10357901diisopropyl (E)-3-acetoxymethyl-4-hydroxybut-1-enylphosphonate

Product 1

HCID 21765581diisopropyl (E)-3-acetoxymethyl-4-t-butyldiphenylsilyloxybut-1-enylphosphonateYield 94.3%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of diisopropyl (E)-3-acetoxymethyl-4-hydroxybut-1-enylphosphonate (3 g, 9.7 mmol ) and imidazole (1.7 g, 25 mmol) in anhydrous THF (60 ml) at 0° C. was added t-butyldiphenylsilylchloride (3.2 ml, 12.7 mmol). After stirring at room temperature for 3 h, the solvent was removed and the residue was partitioned between chloroform (100 ml) and brine (30 ml). The organic phase was dried (MgSo4), evaporated in vacuo and chromatographed on silica gel, eluting with chloroform of increasing polarity to chloroform-methanol (100:1) to give diisopropyl (E)-3-acetoxymethyl-4-t-butyldiphenylsilyloxybut-1-enylphosphonate as an oil (5 g, 94%); υmax (film) 3071, 3050, 2977, 2931, 2858, 1743, 1630, 1582, 1472,and 1425 cm-1 ; δH (CDCl3) 1.05 [9H, s, C(CH3)3 ], 1.26 (3H, d, J 6 Hz, CH3CH), 1.27 (3H, d, J 6 Hz, CH3CH), 1.32 [6H, d, J 6.3 Hz, (CH3)2CH], 1.98 (3H, s, CH3CO), 2.74 (1H, m, CH), 3.72 (2H, m, CH2), 4.22 (2H, m, CH2), 4.65 (2H, m, 2×CH(CH3)2 ], 5.76 (1H, ddd, J 1, 17 and 18 Hz, PCH=CH), 6.99 (1H, ddd, J 7, 17 and 22 Hz, PCH=CH), 7.3-7.7 (10H, m, 2×C6H5) (Found: C, 63.42; H, 8.22%. C29H43O6PSi requires C, 63.71; H, 7.93%.).

Workup

  1. customthe solvent was removed
  2. customthe residue was partitioned between chloroform (100 ml) and brine (30 ml)
  3. customThe organic phase was dried (MgSo4)
  4. customevaporated in vacuo
  5. customchromatographed on silica gel
  6. washeluting with chloroform
  7. temperatureof increasing polarity to chloroform-methanol (100:1)

Sources & evidence

ORD record
ord-5d137eb318c046bcb6dae21e376348e4
Source dataset
uspto-grants-1994_10
Patent number
US05356886

Reaction notes

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