Cesium bicarbonate → (2R)-2-Phenylcarbonyloxypropyl(2S)-2-(tert-Butoxycarbonyl)amino-3-(3,4-dihydroxyphenyl)propanoate

HRID 1023752

반응식

HRID 1023752 반응식
[C:1]([O:9][C@H:10]([CH3:13])[CH2:11]Br)(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C([N+](CCCC)(CCCC)CCCC)CCC.[OH:31][C:32]1[CH:33]=[C:34]([CH2:39][C@H:40]([NH:44][C:45]([O:47][C:48]([CH3:51])([CH3:50])[CH3:49])=[O:46])[C:41]([O-:43])=[O:42])[CH:35]=[CH:36][C:37]=1[OH:38].C(=O)(O)[O-].[Cs+]>CN(C)C(=O)C>[C:48]([O:47][C:45]([NH:44][C@@H:40]([CH2:39][C:34]1[CH:35]=[CH:36][C:37]([OH:38])=[C:32]([OH:31])[CH:33]=1)[C:41]([O:43][CH2:11][C@H:10]([O:9][C:1]([C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1)=[O:8])[CH3:13])=[O:42])=[O:46])([CH3:51])([CH3:49])[CH3:50]

참가 물질

5

반응물 3

HCID 2734983Cesium bicarbonateHCID 46899461(2S)-3-(3,4-Dihydroxyphenyl)-2-[(tert-butoxycarbonyl)amino]propanoic Acid, Tetrabutylammonium SaltHCID 66930925(1R)-2-Bromo-1-methylethyl benzoate

생성물 1

HCID 46899463(2R)-2-Phenylcarbonyloxypropyl(2S)-2-(tert-Butoxycarbonyl)amino-3-(3,4-dihydroxyphenyl)propanoate수율 68%

시약·촉매·용매 1

HCID 31374Dimethylacetamide용매

반응 조건

온도
55 °C

실험 절차

A suspension of (1R)-2-bromo-1-methylethyl benzoate 1b (4.98 g, 20.6 mmol), (2S)-3-(3,4-dihydroxyphenyl)-2-[(tert-butoxycarbonyl)amino]propanoic acid, tetrabutylammonium salt 1a (7.3 g, 25 mmol), and cesium bicarbonate (4.85 g, 25 mmol) in N,N-dimethylacetamide (100 mL) was stirred at 55° C. for 16 h. The solvent was evaporated under vacuum. Ethyl acetate was added to the residue and the resulting solution was washed with water, then 5% NaHCO3 and brine, and dried over Na2SO4. After removing the solvent under reduced pressure, chromatography (silica gel, 30% ethyl acetate in hexane) of the residue gave 6.3 g (68% yield) of the title compound 1c as a white solid. 1H NMR (400 MHz, CD3OD): δ 1.25 (s, 9H), 1.40 (d, J=6.4 Hz, 3H), 2.99 (dd, J=7.6, 14.4 Hz, 1H), 3.10 (dd, J=5.6, 14.4 Hz, 1H), 4.24 (dd, J=5.6, 7.4 Hz, 1H), 4.38 (dd, J=6.8, 11.6 Hz, 1H), 4.52 (dd, J=3.2, 11.6 Hz, 1H), 5.40 (m, 1H), 6.53 (dd, J=2.2, 8.4 Hz, 1H), 6.66 (d, J=2.2 Hz, 1H), 6.69 (d, J=8.4 Hz, 1H), 7.47 (t, J=7.6 Hz, 2H), 7.60 (t, J=7.6 Hz, 1H), 8.02 (d, J=7.6 Hz, 2H). MS (ESI) m/z 360.15 (M+H)+ and 358.09 (M−H)−.

후처리

  1. customThe solvent was evaporated under vacuum
  2. additionEthyl acetate was added to the residue
  3. washthe resulting solution was washed with water
  4. dry with material5% NaHCO3 and brine, and dried over Na2SO4
  5. customAfter removing the solvent under reduced pressure, chromatography (silica gel, 30% ethyl acetate in hexane) of the residue

출처 및 근거

ORD 기록
ord-ab025926ad9d4a28bb833e15931878c7
출처 데이터셋
uspto-grants-2014_05
특허 번호
US08722733B2

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