p-Toluenesulfonic acid → 3-TETRAHYDROPYRANYLOXY-1-TRIMETHYLSILYL-1-PROPYNE

HRID 601788Notes

Reaction equation

[O:1]1[CH:6]=[CH:5][CH2:4][CH2:3][CH2:2]1.CC1C=CC(S(O)(=O)=O)=CC=1.[CH3:18][Si:19]([C:22]#[C:23][CH2:24][OH:25])([CH3:21])[CH3:20]>C([O-])(O)=O.[Na+]>[CH3:18][Si:19]([CH3:21])([CH3:20])[C:22]#[C:23][CH2:24][O:25][CH:6]1[CH2:5][CH2:4][CH2:3][CH2:2][O:1]1

Participants

Conditions

Temperature: 0 °C

Procedure

A 50 mL round bottom flask was charged with dihydropyran, (3.5 mL, 39 mmol) and pTSA, (7 mg, 0.039 mmol) was added. When the pTSA had dissolved, the solution was cooled to 0° C. in an ice bath and 3-(trimethylsilyl)propargyl alcohol, (5.7 mL, 39 mmol) was added dropwise. It was allowed then allowed to warm slowly to room temperature and held for 1 h. The mixture was added to saturated NaHCO3, (250 mL) extracted with Et2O, (150 mL) (×3), washed with brine, (150 mL), dried (Na2SO4) and the solvent was evaporated under reduced pressure. The material was purified by chromatography eluting with heptane-EtOAc, gradient 0 to 10% EtOAc. 8.5 g. 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 0.19 (s, 9H) 0.77-0.94 (m, 1H) 1.49-1.59 (m, 1H) 1.57-1.70 (m, 2H) 1.69-1.93 (m, 2H) 3.35-3.63 (m, 1H) 3.78-3.91 (m, 1H) 4.19-4.35 (m, 2H) 4.82 (t, J=3.34 Hz, 1H).

Workup

additionwas added
temperatureto warm slowly to room temperature
extractionextracted with Et2O, (150 mL) (×3)
washwashed with brine, (150 mL)
dry with materialdried (Na2SO4)
customthe solvent was evaporated under reduced pressure
customThe material was purified by chromatography
washeluting with heptane-EtOAc, gradient 0 to 10% EtOAc

Sources & evidence

ORD record: ord-f5f5459879db4cce88316a6950740aed
Source dataset: uspto-grants-2011_03
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07902252B2

Reaction notes

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