tert-butyl ((2S,3R)-1-((2S,4R)-2-(((1R,2S)-1-((cyclopropylsulfonyl)carbamoyl)-2-vinylcyclopropyl)carbamoyl)-4-hydroxypyrrolidin-1-yl)-3,5-dimethyl-1-oxonon-8-en-2-yl)carbamate → tert-Butyl ((2R,6S,7R,13 aS,14aR,16aS,Z)-14a-((cyclopropylsulfonyl)carbamoyl)-2-hydroxy-7,9-dimethyl-5,16-dioxo-1,2,3,5,6,7,8,9,10,11,13a,14,14a,15,16,16a-hexadecahydrocyclopropa[e]pyrrolo[1,2-a][1,4]diazacyclopentadecin-6-yl)carbamate

HRID 523174

반응식

HRID 523174 반응식
[CH:1]1([S:4]([NH:7][C:8]([C@@:10]2([NH:15][C:16]([C@@H:18]3[CH2:22][C@@H:21]([OH:23])[CH2:20][N:19]3[C:24](=[O:43])[C@@H:25]([NH:35][C:36](=[O:42])[O:37][C:38]([CH3:41])([CH3:40])[CH3:39])[C@H:26]([CH3:34])[CH2:27][CH:28]([CH3:33])[CH2:29][CH2:30][CH:31]=C)=[O:17])[CH2:12][C@H:11]2[CH:13]=C)=[O:9])(=[O:6])=[O:5])[CH2:3][CH2:2]1>ClCCCl.CC1C=C(C)C(N2C(=[Ru](Cl)(Cl)=CC3C=CC=CC=3OC(C)C)N(C3C(C)=CC(C)=CC=3C)CC2)=C(C)C=1>[CH:1]1([S:4]([NH:7][C:8]([C@@:10]23[CH2:12][C@H:11]2[CH:13]=[CH:31][CH2:30][CH2:29][CH:28]([CH3:33])[CH2:27][C@@H:26]([CH3:34])[C@H:25]([NH:35][C:36](=[O:42])[O:37][C:38]([CH3:40])([CH3:39])[CH3:41])[C:24](=[O:43])[N:19]2[CH2:20][C@H:21]([OH:23])[CH2:22][C@H:18]2[C:16](=[O:17])[NH:15]3)=[O:9])(=[O:5])=[O:6])[CH2:3][CH2:2]1

참가 물질

4

반응물 1

HCID 89550268tert-butyl ((2S,3R)-1-((2S,4R)-2-(((1R,2S)-1-((cyclopropylsulfonyl)carbamoyl)-2-vinylcyclopropyl)carbamoyl)-4-hydroxypyrrolidin-1-yl)-3,5-dimethyl-1-oxonon-8-en-2-yl)carbamate

생성물 1

HCID 89550183tert-Butyl ((2R,6S,7R,13 aS,14aR,16aS,Z)-14a-((cyclopropylsulfonyl)carbamoyl)-2-hydroxy-7,9-dimethyl-5,16-dioxo-1,2,3,5,6,7,8,9,10,11,13a,14,14a,15,16,16a-hexadecahydrocyclopropa[e]pyrrolo[1,2-a][1,4]diazacyclopentadecin-6-yl)carbamate

시약·촉매·용매 2

HCID 11763533(1,3-Bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene)(dichloro)((2-((propan-2-yl)oxy)phenyl)methylidene)ruthenium촉매HCID 111,2-Dichloroethane용매

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온도
80 °C

실험 절차

A solution of tert-butyl ((2S,3R)-1-((2S,4R)-2-(((1R,2S)-1-((cyclopropylsulfonyl)carbamoyl)-2-vinylcyclopropyl)carbamoyl)-4-hydroxypyrrolidin-1-yl)-3,5-dimethyl-1-oxonon-8-en-2-yl)carbamate (9.50 g, 15.2 mmol) in DCE (2.5 L) was sparged with nitrogen for 30 min. To the solution was added Hoveyda-Grubbs 2nd Generation Catalyst (0.574 g, 0.912 mmol). The solution was heated at 80° C. for 2 h; then cooled to 45° C. and stirred for 2 days. The reaction solution was concentrated in vacuo and the resulting solid residue was then subjected to flash chromatography on silica gel (hexanes:acetone, 80:20 to 40:60) to afford tert-butyl ((2R,6S,7R,13aS,14aR,16aS,Z)-14a-((cyclopropylsulfonyl)carbamoyl)-2-hydroxy-7,9-dimethyl-5,16-dioxo-1,2,3,5,6,7,8,9,10,11,13a,14,14a,15,16,16a-hexadecahydrocyclopropa[e]pyrrolo[1,2-a][1,4]diazacyclopentadecin-6-yl)carbamate as a solid foam (7 g). MS: MS m/z 597.35 (M++1).

후처리

  1. temperaturethen cooled to 45° C.
  2. concentrationThe reaction solution was concentrated in vacuo

출처 및 근거

ORD 기록
ord-6b6c84a2a7db43c2801b62d335190a80
출처 데이터셋
uspto-grants-2016_05
특허 번호
US09334279B2

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