Potassium Carbonate → diisopropyl (E)-3-(t-butyldiphenylsilyloxy)methyl-4-hydroxybut-1-enylphosphonate

HRID 1708087Notes

Reaction equation

HRID 1708087 reaction equation
C([O:4][CH2:5][CH:6]([CH2:19][O:20][Si:21]([C:34]([CH3:37])([CH3:36])[CH3:35])([C:28]1[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1)[C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1)/[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)C.C(=O)([O-])[O-].[K+].[K+]>CO>[Si:21]([O:20][CH2:19][CH:6]([CH2:5][OH:4])/[CH:7]=[CH:8]/[P:9](=[O:18])([O:14][CH:15]([CH3:16])[CH3:17])[O:10][CH:11]([CH3:12])[CH3:13])([C:34]([CH3:36])([CH3:35])[CH3:37])([C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1)[C:28]1[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1

Participants

4

Reactant 2

HCID 11430Potassium CarbonateHCID 21765581diisopropyl (E)-3-acetoxymethyl-4-t-butyldiphenylsilyloxybut-1-enylphosphonate

Product 1

HCID 10436173diisopropyl (E)-3-(t-butyldiphenylsilyloxy)methyl-4-hydroxybut-1-enylphosphonateYield 73.2%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

A solution of diisopropyl (E)-3-acetoxymethyl-4-t-butyldiphenylsilyloxybut-1-enylphosphonate (5 g, 9.2 mmol) in methanol (50 ml) was stirred with potassium carbonate (63 g, 0.45 mmol) for 5 h at room temperature. The solvent was removed in vacuo and the residue was chromatographed on silica gel eluting with chloroform-methanol (100:1) of increasing polarity to (30:1) to give diisopropyl (E)-3-t-butyldiphenylsilyloxymethyl-4-hydroxybut-1-enylphosphonate as an oil (3.4 g, 73%): υmax (film) 3381, 3071, 3025, 2940, 2931, 2858, 2360, 2332, 1631, 1585, 1471 and 1428 cm-1 ; δH (CDCl3) 1.05 [9H, s, C(CH3)3 ], 1.25 (3H, d, J 6 Hz, CHCH3), 1.27 (3H, d, J 6.1 Hz, CHCH3), 1.31 [6H, d, J 6 Hz, CH(CH3)2 ], 2.15 (1H, t, J 5.9 Hz, D2O exchangeable OH), 2.65 (1H, m, CH), 3.80 (4H, m, 2×CH2), 4.65 [2H, m, 2×CH(CH3)2 ], 5.76 (1H, ddd, J 1, 17 and 19 Hz, PCH=CH), 6.64 (1H, ddd, J 8, 17 and 23 Hz, PCH=CH), 7.4-7.7 (10H, m, 2×C6H5) (Found: C, 63.65; H, 8.16%. M+ 504.2444. C27H41O5PSi.0.25 H2O requires C, 63.69; H, 8.22%. M+ 504.2461).

Workup

  1. customThe solvent was removed in vacuo
  2. customthe residue was chromatographed on silica gel eluting with chloroform-methanol (100:1)
  3. temperatureof increasing polarity to (30:1)

Sources & evidence

ORD record
ord-2939d3bc9010457b8cdff7c78c9b4c25
Source dataset
uspto-grants-1994_10
Patent number
US05356886

Reaction notes

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