Phosphate → HCID 54568601, compound

HRID 651877Notes

Reaction equation

[O:1]1[CH2:6][CH2:5][CH2:4][CH2:3][CH:2]1[O:7][CH:8]=[CH:9][CH2:10][CH2:11][CH2:12][OH:13].[H-].[Na+].[CH3:16][S:17](Cl)(=[O:19])=[O:18].P([O-])([O-])([O-])=O>C1COCC1>[CH3:16][S:17]([O:13][CH2:12][CH2:11][CH2:10][CH:9]=[CH:8][O:7][CH:2]1[CH2:3][CH2:4][CH2:5][CH2:6][O:1]1)(=[O:19])=[O:18]

Participants

Conditions

Temperature: 25 °C

Procedure

The alcohol 106 (147 mg, 0.791 mmol) was added to a suspension of NaH (60% in oil, 38 mg, 0.95 mmol, 1.2 equiv) in THF (5 mL). The resulting mixture was stirred at 25° C. for 30 min and cooled to 0° C. before CH3SO2Cl was added dropwise. The reaction mixture was stirred 15 min at 0° C. and 15 min at 25° C. Phosphate buffer (100 mL, pH 7) was added and the mixture extracted with CH2Cl2 (2×50 mL). The combined organic phase was dried (Na2SO4) and the solvent was removed under vacuum. Chromatography (SiO2, 2×25 cm, 30% EtOAc-hexane containing 2% Et3N) afforded 107 (205 mg, 208 mg theoretical, 98%) as a colorless oil as a mixture of E- and Z-olefin isomers (50:50): 1H NMR (CDCl3, 400 MHz) δ 6.24 (dt, J=12.3, 1.3 Hz, 0.5 H), 6.14 (dt, J=6.3, 1.4 Hz, 0.5H), 5.05 (dt, J=12.3, 7.5 Hz, 0.5H), 4.88 and 4.85 (two t, J=3.1, 3.4 Hz, 1H), 4.43 (m, 0.5H), 4.15 (m, 1H), 3.83 and 3.54 (two m, 2H), 3.05 (s, 3H), 2.17 and 1.98 (two m, 2H), 1.85-1.49 (m, 8H).

Workup

additionwas added dropwise
stirringThe reaction mixture was stirred 15 min at 0° C. and 15 min at 25° C
extractionthe mixture extracted with CH2Cl2 (2×50 mL)
dry with materialThe combined organic phase was dried (Na2SO4)
customthe solvent was removed under vacuum

Sources & evidence

ORD record: ord-ca1c0304babf43fdb8f387c0cb4aa0b0
Source dataset: uspto-grants-2001_08
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US06281354B1

Reaction notes

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