Triethoxysilane → (Z)-dodec-7-enol

To a solution of rhodium(III) chloride trihydrate (1.3 mg, 0.005 mmol), copper(II) nitrate hemipentahydrate (5.8 mg, 0.025 mmol) in THF (2.5 mL) and water (0.5 mL) was added 7-dodecyn-1-ol (91 mg, 0.50 mmol). The solution was stirred for 5 minutes and then triethoxysilane (0.21 g, 0.23 mL, 1.25 mmol) was added. The solution was stirred at room temperature for 8 hours. The volatiles were removed in vacuo and a solution of hexane (5 mL) and ether (1 mL) was added. The solution was dried over magnesium sulfate and filtered through a one inch plug of silica gel. The substrate was diluted with hexane/ether (5:1). The solvent was removed in vacuo. The product was then added to a solution of 3N hydrochloric acid (3 mL) and stirred at room temperature for 1 hour. The aqueous layer was extracted with ether (3×10 mL). The combined organics were dried over magnesium sulfate and filtered. The solvent was removed in vacuo to afford 0.088 g (0.48 mmol, 96%) of Z-7-Dodecen-1-ol which was a 14:1 Z:E mixture by spectroscopic analysis. Spectral analysis of the Z-isomer: IR (neat) 3434.8, 2929.0, 2857.1, 1459.2, 1056.1 cm-1 ; 1H NMR (300 MHz, CDCl3) δ 5.33 (m, 2 H), 3.62 (t, J=6.6 Hz, 2 H), 2.01 (br d, 4 H), 1.66 - 1.5 (m, 2H), 1.33 - 1.22 (m, 11 H), 0.88 (t, J=7 Hz, 3 H); 13C NMR (75 MHz, CDCl3) δ 129.99, 129.67, 62.96, 32.74, 32.49, 31.93, 31.21, 29.69, 29.05, 28.58, 27.10, 26.90, 25.63, 22.32, 18.41, 13.99.

1. stirringThe solution was stirred at room temperature for 8 hours
2. customThe volatiles were removed in vacuo
3. additiona solution of hexane (5 mL) and ether (1 mL) was added
4. dry with materialThe solution was dried over magnesium sulfate
5. filtrationfiltered through a one inch plug of silica gel
6. additionThe substrate was diluted with hexane/ether (5:1)
7. customThe solvent was removed in vacuo
8. additionThe product was then added to a solution of 3N hydrochloric acid (3 mL)
9. stirringstirred at room temperature for 1 hour
10. extractionThe aqueous layer was extracted with ether (3×10 mL)
11. dry with materialThe combined organics were dried over magnesium sulfate
12. filtrationfiltered
13. customThe solvent was removed in vacuo

ORD record

ord-a306b7ddc26c4a3eba977b1fbd687932

Source dataset

uspto-grants-1996_02

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US05492964