Lithium amide → (3S,alphaR)-t-Butyl 3-(N-allyl-alpha-methylbenzylamino)-4-pentenoate

HRID 1637038노트

반응식

HRID 1637038 반응식
[CH2:1]([NH:4][C@H:5]([CH3:12])[C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1)[CH:2]=[CH2:3].C([Li])CCC.[NH2-].[Li+].[C:20]([O:26][C:27]([CH3:30])([CH3:29])[CH3:28])(=[O:25])[CH:21]=[CH:22][CH:23]=[CH2:24]>O1CCCC1>[CH2:1]([N:4]([C@H:5]([CH3:12])[C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1)[C@H:22]([CH:23]=[CH2:24])[CH2:21][C:20]([O:26][C:27]([CH3:29])([CH3:28])[CH3:30])=[O:25])[CH:2]=[CH2:3]

참가 물질

6

반응물 4

HCID 24532Lithium amideHCID 2733823(R)-(+)-N-allyl-alpha-methylbenzylamineHCID 53950126t-Butyl pentadienoateHCID 178418339Butyllithium

생성물 1

HCID 11109854(3S,alphaR)-t-Butyl 3-(N-allyl-alpha-methylbenzylamino)-4-pentenoate수율 85%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매2회

실험 절차

A solution of (R)-N-allyl-α-methylbenzylamine (24) (1.78 g, 11.1 mmol) in anhydrous tetrahydrofuran (20 ml) was cooled to -78° C. and 1.6M butyllithium (6.00 ml, 9.5 mmol) was added dropwise via a syringe. The resulting orange lithium amide solution was stirred at -78° C. for 1 hour. A solution of t-butyl pentadienoate (25) (1.137 g, 7.4 mmol) in anhydrous tetrahydrofuran (15 ml) was then added via a cannula and the solution was stirred for a further 1 hour. The reaction was quenched by the addition of saturated aqueous ammonium chloride solution and the solution was allowed to warm to room temperature. Ethyl acetate (50 ml) was added, followed by brine (10 ml). The organic layer was separated, dried (magnesium sulphate) and filtered and the solvent evaporated under reduced pressure to afford a pale yellow oil. This was purified by flash chromatography on silica gel [ethyl acetate/petroleum ether (1:49)] to afford the title compound (Rf 0.25) as a colourless oil (1.97 g, 85%). δH (300 MHz; CDCl3) 7.40-7.19 (5H, m, Ph), 5.94-5.74 (2H, m, CH2 =CHCH and NCH2CH=CH2), 5.16-5.00 (4H, m, CH2 =CHCH and NCH2CH=CH2), 4.02 (1H, q, J=6.8, PhCHCH3), 3.90 (1H, app. q, J=7.1, NCHCH2), 3.15 (2H, d, J=6.1, NCH2CH=CH2), 2.41 (1H, dd, J=6.4 and 14.5, CH2CO2), 2.31 (1H, dd, J=14.5 and 8.3, CH2CO2), 1.42 (9H, s, (CH3)3C), 1.39 (3H, d, J=6.8, PhCHCH3).

후처리

  1. customThe reaction was quenched by the addition of saturated aqueous ammonium chloride solution
  2. additionEthyl acetate (50 ml) was added
  3. customThe organic layer was separated
  4. dry with materialdried (magnesium sulphate)
  5. filtrationfiltered
  6. customthe solvent evaporated under reduced pressure
  7. customto afford a pale yellow oil
  8. customThis was purified by flash chromatography on silica gel [ethyl acetate/petroleum ether (1:49)]

출처 및 근거

ORD 기록
ord-b5b2668e8c934eaa970d010875a888ec
출처 데이터셋
uspto-grants-2000_03
특허 번호
US06037498

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