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Ethyl Acetate → methyl 5-[2-[(tert-butoxycarbonyl)amino]phenyl]-4-(2-tert-butoxy-2-oxoethyl)-6-cyclohexyl-4H-thieno[3,2-b]pyrrole-2-carboxylate

HRID 1008970
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HRID 1008970 반응식
Br[C:2]1[N:6]([CH2:7][C:8]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:9])[C:5]2[CH:15]=[C:16]([C:18]([O:20][CH3:21])=[O:19])[S:17][C:4]=2[C:3]=1[CH:22]1[CH2:27][CH2:26][CH2:25][CH2:24][CH2:23]1.[C:28]([O:32][C:33](=[O:50])[NH:34][C:35]1[CH:40]=[CH:39][CH:38]=[CH:37][C:36]=1B1OC(C)(C)C(C)(C)O1)([CH3:31])([CH3:30])[CH3:29].C([O-])([O-])=O.[Na+].[Na+].CCOC(C)=O>O1CCOCC1.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[C:28]([O:32][C:33]([NH:34][C:35]1[CH:40]=[CH:39][CH:38]=[CH:37][C:36]=1[C:2]1[N:6]([CH2:7][C:8]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:9])[C:5]2[CH:15]=[C:16]([C:18]([O:20][CH3:21])=[O:19])[S:17][C:4]=2[C:3]=1[CH:22]1[CH2:27][CH2:26][CH2:25][CH2:24][CH2:23]1)=[O:50])([CH3:31])([CH3:29])[CH3:30]
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참가 물질

7

반응물 4

HCID 8857Ethyl AcetateHCID 10340Sodium CarbonateHCID 2773231tert-Butyl (2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)carbamateHCID 67298685methyl 5-bromo-4-(2-tert-butoxy-2-oxoethyl)-6-cyclohexyl-4H-thieno[3,2-b]pyrrole-2-carboxylate

생성물 1

HCID 67298849methyl 5-[2-[(tert-butoxycarbonyl)amino]phenyl]-4-(2-tert-butoxy-2-oxoethyl)-6-cyclohexyl-4H-thieno[3,2-b]pyrrole-2-carboxylate
수율 89%

시약·촉매·용매 2

HCID 178418476HCID 178418476, 화합물촉매HCID 312751,4-Dioxane용매

실험 절차

A solution (0.15 M) of methyl 5-bromo-4-(2-tert-butoxy-2-oxoethyl)-6-cyclohexyl-4H-thieno[3,2-b]pyrrole-2-carboxylate (from Step 2) in dioxane was treated with tert-butyl-N-[2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]carbamate (1.5 eq.) and 2 N Na2CO3 solution (6 eq.) and degassed. PdCl2(PPh3)2 (0.2 eq.) was added and the suspension refluxed for 30 mins. After cooling, EtOAc was added and the solution was washed with water, brine, dried over sodium sulfate and evaporated in vacuo to give a residue which was purified by flash chromatography (PE:EtOAc, 95:5) to afford the title compound (89%) as a solid. 1H-NMR (400 MHz, DMSO-d6, 300 K, δ) 8.00 (s, 1H), 7.73 (m, 2H), 7.47-7.43 (t, J 8.6, 1H), 7.27-7.23 (m, 2H), 4.73-4.49 (dd, J 20, 2H), 3.82 (s, 3H), 2.17-2.11 (m, 1H), 1.82-1.21 (m, 10H), 1.37 (s, 9H), 1.28 (s, 9H). MS (ES+) m/z: 569 [M+H]+.

후처리

  1. customdegassed
  2. temperaturethe suspension refluxed for 30 mins
  3. temperatureAfter cooling
  4. washthe solution was washed with water, brine
  5. dry with materialdried over sodium sulfate
  6. customevaporated in vacuo
  7. customto give a residue which
  8. customwas purified by flash chromatography (PE:EtOAc, 95:5)

출처 및 근거

ORD 기록
ord-1ca3c3d3ed06468b857172805bd6eb1f
출처 데이터셋
uspto-grants-2011_07
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US07973026B2

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