ethyl 1(R)-[1-[2(S)-(tert-butoxycarbonylamino)-3-[N-cyclopropyl-N-(pent-4-enyl)amino]propanoyl]-4(R)-(tert-butyldimethylsilyloxy)pyrrolidine-2(S)-carboxamido]-2(S)-vinylcyclopropanecarboxylate → HCID 86612090、化合物

HRID 500413

反応式

HRID 500413 の反応式
[C:1]([O:5][C:6]([NH:8][C@@H:9]([CH2:38][N:39](C1CC1)[CH2:40][CH2:41][CH2:42][CH:43]=[CH2:44])[C:10]([N:12]1[CH2:16][C@H:15]([O:17][Si:18]([C:21]([CH3:24])([CH3:23])[CH3:22])([CH3:20])[CH3:19])[CH2:14][C@H:13]1[C:25]([NH:27][C@:28]1([C:33]([O:35][CH2:36][CH3:37])=[O:34])[CH2:30][C@H:29]1C=C)=[O:26])=[O:11])=[O:7])([CH3:4])([CH3:3])[CH3:2]>C(Cl)Cl.CC1C=C(C)C(N2C(=[Ru](Cl)(Cl)=CC3C=CC=CC=3)N(C3C(C)=CC(C)=CC=3C)CC2)=C(C)C=1.C1CCC(P(C2CCCCC2)C2CCCCC2)CC1>[C:1]([O:5][C:6]([NH:8][C@@H:9]1[C:10](=[O:11])[N:12]2[C@@H:13]([CH2:14][C@@H:15]([O:17][Si:18]([C:21]([CH3:23])([CH3:22])[CH3:24])([CH3:19])[CH3:20])[CH2:16]2)[C:25](=[O:26])[NH:27][C@@:28]2([C:33]([O:35][CH2:36][CH3:37])=[O:34])[C@@H:30]([CH2:29]2)[CH:44]=[CH:43][CH2:42][CH2:41][CH2:40][NH:39][CH2:38]1)=[O:7])([CH3:3])([CH3:2])[CH3:4]

参加物

4

反応物 1

HCID 67331048ethyl 1(R)-[1-[2(S)-(tert-butoxycarbonylamino)-3-[N-cyclopropyl-N-(pent-4-enyl)amino]propanoyl]-4(R)-(tert-butyldimethylsilyloxy)pyrrolidine-2(S)-carboxamido]-2(S)-vinylcyclopropanecarboxylate

生成物 1

HCID 86612090HCID 86612090、化合物収率 64.4%

試薬・触媒・溶媒 2

HCID 11147261(1,3-Dimesitylimidazolidin-2-ylidene)(tricyclohexylphosphine)benzylidene ruthenium dichloride触媒HCID 6344Dichloromethane溶媒

実験手順

To a solution of ethyl 1(R)-[1-[2(S)-(tert-butoxycarbonylamino)-3-[N-cyclopropyl-N-(pent-4-enyl)amino]propanoyl]-4(R)-(tert-butyldimethylsilyloxy)pyrrolidine-2(S)-carboxamido]-2(S)-vinylcyclopropanecarboxylate (1.45 g, 2.14 mmoL) in 1 L of methylene chloride was added 181 mg (0.21 mmoL) of Grubb's 2nd generation catalyst [(1,3-Bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium]. The mixture was heated at reflux for 1 h. A second fraction of the catalyst (50 mg, 0.058 mmol) was added, and the mixture was stirred at rt overnight. The residue was concentrated in vacuo, and then purified by flash chromatography eluting with 50% ether/hexane to give 0.84 g (62%) of (1S,4R,6S,14S,18R)-7-cis-14-tert-Butoxycarbonylamino-18-(tert-butyldimethylsilyloxy)-2,15-dioxo-3,12,16-triazatricyclo[14.3.0.04,6]nonadec-7-ene-4-carboxylic acid, ethyl ester as a white solid: LC-MS (Phenomenex 10 μm C18HPLC column: 3.0×50 mm length. Gradient: 100% Solvent A/0% Solvent B to 0% Solvent A/100% Solvent B. Gradient time: 2 min. Hold time: 1 min. Flow rate: 5 mL/min. Detector Wavelength: 220 nM. Solvent A: 10% MeOH/90% H2O/0.1% TFA. Solvent B: 10% H2O/90% MeOH/0.1% TFA.) (Retention time: 2.43 min), MS m/z 649 (M++1).

後処理

  1. temperatureThe mixture was heated
  2. temperatureat reflux for 1 h
  3. concentrationThe residue was concentrated in vacuo
  4. custompurified by flash chromatography
  5. washeluting with 50% ether/hexane

出典と根拠

ORDレコード
ord-cdd241aa466a4cabb90bd727abae591c
出典データセット
uspto-grants-2010_08
特許番号
US07772183B2

関連ノート

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