Trimethylamine oxide → HCID 20565102, compound

Temperature

0 °C

To a mixture of 9.2 g of sodium borohydride and 45.8 g of 2-methyl-2-butene in 350 ml of dry tetrahydrofuran at 0° C. with stirring under nitrogen is added, over 20 minutes, 41.1 ml of boron trifluoride etherate. After 3 hours, to this resulting solution of diisoamylborane is added 38.8 g of 1R,2S(and 1S, 2R)-1-ethynyl-1-trimethylsilyloxy-2-butylcyclopentane in 40 ml of tetrahydrofuran in 20 minutes. The mixture is stirred 2 hours and then stored at -20° C. overnight. The mixture is allowed to warm to 0° C. and at 0° C. 85 g of dry trimethylamineoxide is added portionwise over 20 minutes. After stirring at 25° C. for one hour, the mixture is filtered through diatomaceous earth. The filtrate is poured simultaneously with a solution of 230 g of iodine in 250 ml of tetrahydrofuran into a stirred, cold solution of 430 g of sodium hydroxide in 1900 ml of water. After stirring for 30 minutes, the organic layer is separated. The aqueous layer is extracted with ether. The combined organic solutions are washed twice with a saturated solution of sodium thiosulfate and once with brine. The solution is dried over magnesium sulfate, the solvent is removed and the residue is dissolved in hexane. The hexane solution is filtered through diatomaceous earth and silica gel. The hexane is removed and the residue is purified by dry column chromatography on silica gel eluting with hexane: 45.35 g of 1R,2S(and 1S, 2R)-1-trans-2-iodovinyl)-1-trimethylsilyloxy-2-butylcyclopentane is obtained.

1. additionis added, over 20 minutes
2. stirringThe mixture is stirred 2 hours
3. waitstored at -20° C. overnight
4. stirringAfter stirring at 25° C. for one hour
5. filtrationthe mixture is filtered through diatomaceous earth
6. additionThe filtrate is poured simultaneously with a solution of 230 g of iodine in 250 ml of tetrahydrofuran into a stirred, cold solution of 430 g of sodium hydroxide in 1900 ml of water
7. stirringAfter stirring for 30 minutes
8. customthe organic layer is separated
9. extractionThe aqueous layer is extracted with ether
10. washThe combined organic solutions are washed twice with a saturated solution of sodium thiosulfate and once with brine
11. dry with materialThe solution is dried over magnesium sulfate
12. customthe solvent is removed
13. dissolutionthe residue is dissolved in hexane
14. filtrationThe hexane solution is filtered through diatomaceous earth and silica gel
15. customThe hexane is removed
16. customthe residue is purified
17. dry with materialby dry column chromatography on silica gel eluting with hexane

ORD record

ord-bf81dbf5b7be491eb82639b91a5461a2

Source dataset

uspto-grants-1979_05

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US04154954