3-Boc-2,2-dimethyloxazolidine-4-carboxaldehyde, (S)-(-)- → tert-butyl (4S)-4-[(1R)-1-hydroxyprop-2-en-1-yl]-2,2-dimethyl-1,3-oxazolidine-3-carboxylate

HRID 2200834노트

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HRID 2200834 반응식
[C:1]([O:5][C:6]([N:8]1[C@H:12]([CH:13]=[O:14])[CH2:11][O:10][C:9]1([CH3:16])[CH3:15])=[O:7])([CH3:4])([CH3:3])[CH3:2].[CH:17]([Mg]Br)=[CH2:18]>C1COCC1>[C:1]([O:5][C:6]([N:8]1[C@H:12]([C@H:13]([OH:14])[CH:17]=[CH2:18])[CH2:11][O:10][C:9]1([CH3:16])[CH3:15])=[O:7])([CH3:4])([CH3:3])[CH3:2]

참가 물질

4

반응물 2

HCID 1798243-Boc-2,2-dimethyloxazolidine-4-carboxaldehyde, (S)-(-)-HCID 178418507HCID 178418507, 화합물

생성물 1

HCID 10777541tert-butyl (4S)-4-[(1R)-1-hydroxyprop-2-en-1-yl]-2,2-dimethyl-1,3-oxazolidine-3-carboxylate수율 62%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매2회

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온도
-78 °C

실험 절차

To a −78° C. solution of (S)-Garner aldehyde (3, 7.0 g, 30.5 mmol) in dry THF (50 mL) under N2 was slowly added vinylmagnesium bromide (92 mL, 92 mmol, a 1 M solution in THF) via cannula. After the cloudy yellow solution was stirred for 2 h at −78° C., it was warmed to 0° C., and the reaction was quenched with saturated aqueous NH4Cl solution (60 mL). The product was extracted with Et2O (2×60 mL). The combined organic layers were washed with brine (60 mL), dried (Na2SO4), and concentrated. The mixture of erythro and threo diastereomers was separated by column chromatography by gravity (hexane/EtOAc 5:1) to afford 4 (4.8 g, 62%) and its C3-epimer 4a (0.8 g, 10.2%). Compound 4: [α]25D −37.7° (c 1.8, CHCl3); Rf 0.26 (EtOAc/hexane 1:3); 1H NMR (CDCl3) δ 1.48 (s, 3H), 1.50 (s, 9H), 1.58 (s, 3H), 3.91 (m, 2H), 3.98 (m, 1H), 4.25 (m, 1H), 4.39 (m, 1H), 5.24 (m, 1H), 5.38 (m, 1H), 5.85 (m, 1H); 13C NMR (CDCl3) δ 24.2, 26.3, 28.3, 61.8, 64.4, 73.3, 81.4, 94.4, 116.1, 117.8, 137.6, 155.0; ESI-HRMS [M+Na]+ C13H23NO4Na calcd for m/z 280.1525, found 280.1519.

후처리

  1. customTo a −78° C.
  2. temperatureit was warmed to 0° C.
  3. customthe reaction was quenched with saturated aqueous NH4Cl solution (60 mL)
  4. extractionThe product was extracted with Et2O (2×60 mL)
  5. washThe combined organic layers were washed with brine (60 mL)
  6. dry with materialdried (Na2SO4)
  7. concentrationconcentrated
  8. additionThe mixture of erythro and threo diastereomers
  9. customwas separated by column chromatography by gravity (hexane/EtOAc 5:1)

출처 및 근거

ORD 기록
ord-049369a942de431fabd6a234eb0a5b15
출처 데이터셋
uspto-grants-2016_06
특허 번호
US09359389B2

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