Carbon Dioxide → (1R,5R)-3,5,8,8-Tetramethyl-2,4-dioxo-3-azabicyclo[3.2.1]octane-1-carboxylic acid

HRID 1258120노트

반응식

HRID 1258120 반응식
[CH3:1][C@:2]12[C:9]([CH3:11])([CH3:10])[CH:6]([CH2:7][CH2:8]1)[C:5](=[O:12])[N:4]([CH3:13])[C:3]2=[O:14].N[C@H](C(O)=O)C[SeH].[Li]CCCC.C1CCCCC1.[C:33](=[O:35])=[O:34]>C1COCC1>[CH3:13][N:4]1[C:3](=[O:14])[C@@:2]2([CH3:1])[C:9]([CH3:10])([CH3:11])[C@:6]([C:33]([OH:35])=[O:34])([CH2:7][CH2:8]2)[C:5]1=[O:12]

참가 물질

7

반응물 5

HCID 280Carbon DioxideHCID 8078CyclohexaneHCID 25076L-SelenocysteineHCID 57518626(1R)-1,3,8,8-Tetramethyl-3-azabicyclo[3.2.1]octane-2,4-dioneHCID 178418339Butyllithium

생성물 1

HCID 15260531(1R,5R)-3,5,8,8-Tetramethyl-2,4-dioxo-3-azabicyclo[3.2.1]octane-1-carboxylic acid

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매

반응 조건

온도
-95 °C

실험 절차

To a solution of step 2 intermediate (2 g, 10.2 mmol) in THF maintained at −95° C. under N2 atmosphere, 1.2N Sec.BuLi in cyclohexane (9.5 mL, 13.3 mmol) was added. After stirring for 15 min at −95° C., small pieces of dry ice (2 g) were added and the reaction mixture was kept at this temperature for 1 h before quenching with water (3 mL). The reaction mixture was allowed to warm to room temperature. To this 5% NaHCO3 solution (100 mL) and diethyl ether (50 mL) was added, the aqueous layer was separated and acidified with KHSO4 to pH 2. This was extracted again with diethyl ether, washed with brine, dried with anhydrous Na2SO4 and concentrated. (1.85 g). 1H NMR (400 MHz, CDCl3) δ ppm: 1.0 (s, 3H), 1.1 (s, 3H), 1.26 (s, 3H), 1.88-1.98 (m, 2H), 2.64-2.72 (m, 1H), 2.8 (m, 1H), 3.13 (s, 3H). m/z (M−H): 238.

후처리

  1. waitthe reaction mixture was kept at this temperature for 1 h
  2. custombefore quenching with water (3 mL)
  3. temperatureto warm to room temperature
  4. additionTo this 5% NaHCO3 solution (100 mL) and diethyl ether (50 mL) was added
  5. customthe aqueous layer was separated
  6. extractionThis was extracted again with diethyl ether
  7. washwashed with brine
  8. dry with materialdried with anhydrous Na2SO4
  9. concentrationconcentrated

출처 및 근거

ORD 기록
ord-9c9e73429ac34d2d8fa123b4383a11c9
출처 데이터셋
uspto-grants-2013_06
특허 번호
US08466145B2

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