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Tert-butyl cyclopent-2-en-1-yl carbonate → HCID 117974230, 화합물

HRID 58958
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HRID 58958 반응식
[C:1]([O:5][C:6]([N:8]([C@H:16]1[CH2:24][O:23][CH2:22][C@H:21]([CH2:25][C:26]2[C:35]3[C:30](=[CH:31][CH:32]=[CH:33][CH:34]=3)[CH:29]=[CH:28][CH:27]=2)[C@@H:20]([OH:36])[C@H:19]([CH3:37])[O:18][C:17]1=[O:38])[C:9](=[O:15])[O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:7])([CH3:4])([CH3:3])[CH3:2].C(=O)(O[CH:46]1[CH2:50][CH2:49][CH:48]=[CH:47]1)OC(C)(C)C>C1(C)C=CC=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.[Fe+2]>[C:11]([O:10][C:9]([N:8]([C@H:16]1[CH2:24][O:23][CH2:22][C@H:21]([CH2:25][C:26]2[C:35]3[C:30](=[CH:31][CH:32]=[CH:33][CH:34]=3)[CH:29]=[CH:28][CH:27]=2)[C@@H:20]([O:36][CH:50]2[CH2:49][CH2:48][CH:47]=[CH:46]2)[C@H:19]([CH3:37])[O:18][C:17]1=[O:38])[C:6](=[O:7])[O:5][C:1]([CH3:2])([CH3:3])[CH3:4])=[O:15])([CH3:13])([CH3:14])[CH3:12]
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참가 물질

6

반응물 2

HCID 11469477Tert-butyl cyclopent-2-en-1-yl carbonateHCID 117974424tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8R,9S)-8-hydroxy-9-methyl-7-(1-naphthylmethyl)-2-oxo-1,5-dioxonan-3-yl]carbamate

생성물 1

HCID 117974230HCID 117974230, 화합물수율 89%

시약·촉매·용매 3

HCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)촉매
HCID 9811564
Bis(dibenzylideneacetone)palladium
촉매
HCID 1140Toluene용매

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온도
95 °C

실험 절차

To a solution of tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8R,9S)-8-hydroxy-9-methyl-7-(1-naphthylmethyl)-2-oxo-1,5-dioxonan-3-yl]carbamate (205 mg, 0.387 mmol), [Pd2(dba)3] (26.6 mg, 0.029 mmol), and dppf (32.5 mg, 0.058 mmol) in toluene (1.94 mL) was added (E) tert-butyl cyclopent-2-en-1-yl carbonate (250 mg, 1.355 mmol), and the mixture was warmed to 95° C. and stirred for 2 h. An additional portion of (E)-tert-butyl pent-2-en-1-yl carbonate (150 mg, 0.6 equiv.) was added to the reaction and stirring continued for an additional 2 h. The mixture was cooled to room temperature and the toluene was removed under reduced pressure. The residue was dissolved in CH2Cl2 (12 mL), adsorbed to Celite® and purified by flash chromatography (SiO2, 35 mL/min, 0→25 EtOAc/hexanes) to provide tert-butyl N-tert-butoxycarbonyl-N-[(3S,7S,8R,9S)-8-cyclopent-2-en-1-yloxy-9-methyl-7-(1-naphthylmethyl)-2-oxo-1,5-dioxonan-3-yl]carbamate (205 mg, 89%) as a mixture of diastereomers (about 1:1) in the form of a white solid: IR (thin film) 2928, 1755, 1709, 1117 cm−1; 1H NMR (400 MHz, CDCl3) δ 8.09 (m, 1H), 7.82 (m, 1H), 7.74-7.66 (m, 1H), 7.53-7.39 (m, 2H), 7.42-7.28 (m, 2H), 6.13-6.01 (m, 1.5H), 6.01-5.92 (m, 0.5H), 5.07 (app t, J=7.7 Hz, 1H), 4.90-4.79 (m, 2H), 4.02-3.83 (m, 2H), 3.76 (dd, J=13.6, 2.8 Hz, 1H), 3.55-3.39 (m, 3H), 2.82-2.66 (m, 1H), 2.60-2.47 (m, 1H), 2.34-2.17 (m, 2H), 2.11-1.92 (m, 3H), 1.57 (app dd, J=12.6, 6.4 Hz, 3H), 1.39 (app d, J=5.9 Hz, 18H); ESIMS m/z 618 ([M+Na]+).

후처리

  1. stirringstirring
  2. waitcontinued for an additional 2 h
  3. temperatureThe mixture was cooled to room temperature
  4. customthe toluene was removed under reduced pressure
  5. dissolutionThe residue was dissolved in CH2Cl2 (12 mL)
  6. custompurified by flash chromatography (SiO2, 35 mL/min, 0→25 EtOAc/hexanes)

출처 및 근거

ORD 기록
ord-74e060a5873c4480b8886250bc5f2ece
출처 데이터셋
uspto-grants-2016_09
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US09439422B2

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