Tricyclohexylphosphine → 14-Tert-butoxycarbonylamino-18-(tert-butyl-dimethyl-silanyloxy)-2,15-dioxo-3,16-diaza-tricyclo[14.3.0.04,6]nonadec-7-ene-4-carboxylic acid ethyl ester

HRID 500370

반응식

HRID 500370 반응식
[CH2:1]([O:3][C:4]([C:6]1([NH:11][C:12]([CH:14]2[CH2:18][CH:17]([O:19][Si:20]([C:23]([CH3:26])([CH3:25])[CH3:24])([CH3:22])[CH3:21])[CH2:16][N:15]2[C:27](=[O:44])[CH:28]([NH:36][C:37]([O:39][C:40]([CH3:43])([CH3:42])[CH3:41])=[O:38])[CH2:29][CH2:30][CH2:31][CH2:32][CH2:33]C=C)=[O:13])[CH2:8][CH:7]1[CH:9]=[CH2:10])=[O:5])[CH3:2].C1(P(C2CCCCC2)C2CCCCC2)CCCCC1>C(Cl)Cl>[CH2:1]([O:3][C:4]([C:6]12[CH2:8][CH:7]1[CH:9]=[CH:10][CH2:33][CH2:32][CH2:31][CH2:30][CH2:29][CH:28]([NH:36][C:37]([O:39][C:40]([CH3:42])([CH3:43])[CH3:41])=[O:38])[C:27](=[O:44])[N:15]1[CH:14]([CH2:18][CH:17]([O:19][Si:20]([C:23]([CH3:24])([CH3:26])[CH3:25])([CH3:21])[CH3:22])[CH2:16]1)[C:12](=[O:13])[NH:11]2)=[O:5])[CH3:2]

참가 물질

4

반응물 2

HCID 75806TricyclohexylphosphineHCID 673297921-{[1-(2-Tert-butoxycarbonylamino-non-8-enoyl)-4-(tert-butyldimethyl-silanyloxy)-pyrrolidine-2-carbonyl]-amino}-2-vinylcyclopropanecarboxylic acid ethyl ester

생성물 1

HCID 6733002714-Tert-butoxycarbonylamino-18-(tert-butyl-dimethyl-silanyloxy)-2,15-dioxo-3,16-diaza-tricyclo[14.3.0.04,6]nonadec-7-ene-4-carboxylic acid ethyl ester수율 96.3%

시약·촉매·용매 1

HCID 6344Dichloromethane용매

실험 절차

To a solution of 1-{[1-(2-tert-butoxycarbonylamino-non-8-enoyl)-4-(tert-butyl-dimethyl-silanyloxy)-pyrrolidine-2-carbonyl]-amino}-2-vinyl-cyclopropanecarboxylic acid ethyl ester (1.63 g, 2.56 mmoL) in 640 mL of methylene chloride was added 215 mg (0.26 mmoL) of tricyclohexylphosphine[1,3-bis(2,4,6-tri[benzylidene]ruthenium(IV)dichloride. The mixture was heated at reflux for 15 min. The residue was concentrated in vacuo, and then purified by flash chromatography eluting with 30% ethyl acetate/hexane. To further decolorize the sample, the crude product was chromatographed a second time eluting with 50% ether in hexane to give 1.5 g (96%) of 14-tert-butoxycarbonylamino-18-(tert-butyl-dimethyl-silanyloxy)-2,15-dioxo-3,16-diaza-tricyclo[14.3.0.04,6]nonadec-7-ene-4-carboxylic acid ethyl ester as a white solid. 1H NMR (500 MHz, CD3Cl) δ 0.06 (s, 3 H), 0.07 (s, 3H), 0.86 (s, 9H), 1.18-1.24 (m, 6H), 1.34-1.64 (m, 14H), 1.86-1.96 (m, 3H), 2.02-2.09 (m, 1H), 2.11-2.17 (m, 1H), 2.19-2.28 (m, 1H), 2.57-2.63 (m, 1H), 3.50-3.54 (m, 1H), 3.71 (dd, J=10.22, 6.26Hz, 1H), 4.06-4.17 (m, 2H), 4.52-4.58 (m, 2H), 4.75 (d, J=8.55Hz, 1H), 5.21 (t, J=9.92Hz, 1H), 5.35 (d, J=7.63Hz, 1H), 5.45-5.50 (m, 1H), 6.94 (s, 1H); MS m/z 608 (M++1).

후처리

  1. temperatureThe mixture was heated
  2. temperatureat reflux for 15 min
  3. concentrationThe residue was concentrated in vacuo
  4. custompurified by flash chromatography
  5. washeluting with 30% ethyl acetate/hexane
  6. customthe crude product was chromatographed a second time
  7. washeluting with 50% ether in hexane

출처 및 근거

ORD 기록
ord-23a154c132af4ed2bdf731f9a5e7b568
출처 데이터셋
uspto-grants-2010_08
특허 번호
US07772183B2

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