Reaction #1005935

Reaction equation

ethyl acetate

lithium-aluminum hydride

2-butin-1-ol

tri(n-butyl)stannyl-methanolate

→

(Z)-3-Tributylstannanyl-but-2-en-1-ol

Solvents

water

THF

THF

methanol

Conditions

Workup

1. 1
   Otherhas been lowered to 0° C.
2. 2
   workup.STIRRINGStirring
3. 3
   workup.STIRRINGwhile stirring
4. 4
   OtherA strongly exothermic reaction
5. 5
   workup.STIRRINGStirring
6. 6
   workup.WAITwas continued for 10 min
7. 7
   Temperaturewithout cooling
8. 8
   workup.STIRRINGwhile stirring
9. 9
   workup.STIRRINGStirring
10. 10
    workup.WAITwas continued for 2 d at 4° C
11. 11
    workup.WAITwas continued for 1 h at ambient temperature
12. 12
    Extractionextracted thrice with 150 ml diethyl ether each, the combined extracts
13. 13
    Washwere washed twice with 80 ml of water each, then once with 40 ml saturated aqueous sodium chloride solution
14. 14
    Dryingdried with sodium sulfate
15. 15
    Concentrationconcentrated in vacuo
16. 16
    OtherYield 48.6 g oil, which have been purified by chromatography on 300 g silica gel with hexane/MTBE (10:1)

Procedure

To 156.9 ml (156.9 mmol) of a 1 molar solution of lithium-aluminum-hydride in THF 0.77 g (14.3 mmol) sodium methylate have been added and the temperature has been lowered to 0° C. afterwards. Then a solution of 10.0 g (142.7 mmol) 2-butin-1-ol in 108 ml THF has been added dropwise with stirring at this temperature. Stirring was continued for 36 h at 4° C. Thereafter, at about 0° C., 28.6 ml (292.5 mmol) ethyl acetate was-added slowly while stirring. A strongly exothermic reaction was observed. Stirring was continued for 10 min without cooling. After cooling to about 0° C., 45.8 g (142.7 mmol) tri(n-butyl)stannyl-methanolate have been added dropwise while stirring. Stirring was continued for 2 d at 4° C. After addition of 112.9 g methanol stirring was continued for 1 h at ambient temperature. The reaction mixture was poured into 250 ml of water, extracted thrice with 150 ml diethyl ether each, the combined extracts were washed twice with 80 ml of water each, then once with 40 ml saturated aqueous sodium chloride solution, dried with sodium sulfate and concentrated in vacuo. Yield 48.6 g oil, which have been purified by chromatography on 300 g silica gel with hexane/MTBE (10:1). Final yield 34.6 g (67%) oil. δ=0.90 (m); 1.30 (m); 1.50 m); 1.97 (s); 4.02 (t); 6.27 (t).

Source