반응 #710552

반응 방정식

triethylamine

tert-butyl 3-(tert-butyldimethyl-silyloxy)-2-hydroxypropylcarbamate

oxalyl chloride

DMSO

→

tert-butyl 3-(tert-butyldimethylsilyloxy)-2-oxopropylcarbamate

수율 92.0%

용매

CH2Cl2

CH2Cl2

반응 조건

후처리

1. 1
   workup.ADDITIONAfter complete addition the resulting solution
2. 2
   workup.STIRRINGStirring
3. 3
   workup.ADDITIONwas added
4. 4
   기타The cooling bath was removed
5. 5
   온도to warm to room temperature
6. 6
   기타The reaction mixture was partitioned between water (100 mL) and CH2Cl2 (70 mL)
7. 7
   추출the aqueous layer was extracted with further CH2Cl2 (2×70 mL)
8. 8
   건조the combined organics were dried over Na2SO4
9. 9
   농축concentrated under a stream of nitrogen gas
10. 10
    기타The crude residue was purified over silica gel eluting with 5% ethylacetate in n-hexane

실험 절차

To a stirring solution of oxalyl chloride (13.6 mL, 0.16 mol) in dry CH2Cl2 (150 mL) at −78° C. under N2 was added DMSO (15.2 mL, 0.21 mol) dropwise over 30 min. After complete addition the resulting solution was stirred at −78° C. for 1 h. A solution of tert-butyl 3-(tert-butyldimethyl-silyloxy)-2-hydroxypropylcarbamate (32.6 g, 0.11 mol) in CH2Cl2 (50 mL) was then added dropwise over 20 min. Stirring was continued for a further 1 hour at which time triethylamine (59.6 mL, 0.43 mol) was added. The cooling bath was removed and the reaction mixture was allowed to warm to room temperature. The reaction mixture was partitioned between water (100 mL) and CH2Cl2 (70 mL) and the aqueous layer was extracted with further CH2Cl2 (2×70 mL); the combined organics were dried over Na2SO4 and concentrated under a stream of nitrogen gas. The crude residue was purified over silica gel eluting with 5% ethylacetate in n-hexane to give tert-butyl 3-(tert-butyldimethylsilyloxy)-2-oxopropylcarbamate (29.8 g, 92%) as a pale yellow oil. 1H-NMR (300 MHz; CDCl3) δ ppm: 0.11 (6H, s), 0.94 (9H, s), 1.47 (9H, s), 3.92 (2H, s), 4.26 (2H, d, J 4.6 Hz), 5.22 (1H, br s).

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