Acetoacetic Acid → (11s,11As)-7,8-dimethoxy-2-oxo-11-(tert-butyldimethylsilyloxymethyl)-10-(2,2,2-trichloroethoxycarbonyl)-1,2,3,10,11,11a-hexahydro-5h-pyrrolo [2,1-c][1,4]benzodiazepin-5-one

HRID 18866

반응식

HRID 18866 반응식
CC(CC(O)=O)=O.N=O.CC1(C)CCCC(C)(C)N1.[CH3:20][O:21][C:22]1[C:23]([O:55][CH3:56])=[CH:24][C:25]2[N:31]([C:32]([O:34][CH2:35][C:36]([Cl:39])([Cl:38])[Cl:37])=[O:33])[C@H:30]([CH2:40][O:41][Si:42]([C:45]([CH3:48])([CH3:47])[CH3:46])([CH3:44])[CH3:43])[C@@H:29]3[CH2:49][C@@H:50]([OH:52])[CH2:51][N:28]3[C:27](=[O:53])[C:26]=2[CH:54]=1>C(Cl)Cl>[CH3:20][O:21][C:22]1[C:23]([O:55][CH3:56])=[CH:24][C:25]2[N:31]([C:32]([O:34][CH2:35][C:36]([Cl:39])([Cl:37])[Cl:38])=[O:33])[C@H:30]([CH2:40][O:41][Si:42]([C:45]([CH3:48])([CH3:47])[CH3:46])([CH3:44])[CH3:43])[C@@H:29]3[CH2:49][C:50](=[O:52])[CH2:51][N:28]3[C:27](=[O:53])[C:26]=2[CH:54]=1

참가 물질

5

반응물 3

HCID 96Acetoacetic AcidHCID 66670125(11s,11As,2r)-7,8-dimethoxy-2-hydroxy-11-(tert-butyldimethylsilyloxymethyl)-10-(2,2,2-trichloroethoxycarbonyl)-1,2,3,10,11,11a-hexahydro-5h-pyrrolo[2,1-c][1,4]benzodiazepin-5-oneHCID 666701942,2,6,6-Tetramethylpiperidine nitroxyl

생성물 1

HCID 66670095(11s,11As)-7,8-dimethoxy-2-oxo-11-(tert-butyldimethylsilyloxymethyl)-10-(2,2,2-trichloroethoxycarbonyl)-1,2,3,10,11,11a-hexahydro-5h-pyrrolo [2,1-c][1,4]benzodiazepin-5-one

시약·촉매·용매 1

HCID 6344Dichloromethane용매

실험 절차

Diodobenzene diacetate (2.44 g, 7.58 mmol, 1.78 Equiv.) and 2,2,6,6-tetramethylpiperidine nitroxyl (TEMPO) (133 mg, 0.85 mmol, 0.2 Equiv.) were added to a stirred solution of 25 (2.49 g, 4.26 mmol; 1.0 Equiv.) in dry DCM (40 mL). The mixture was stirred at room temperature for 18 h and the reaction mixture was diluted with DAM (50 mL). The organic phase was washed with said sodium bisulphite (2×25 mL), brine (40 mL), dried (MgSO4) and concentrated in vacuo. Purification by flash chromatography (EtOAc/Petroleum ether 6:4) afforded 26 as a white glass. (2.26 g, 91%): [α]D22=+95.0° (c=0.795, CHCl3); 1H NMR (CDCl3, 500 MHz) δ 0.22, 0.23 (two s, 6H, Si(CH3)2), 0.86 (s, 9H, C(CH3)3), 2.56 (dd, 1H, J=3.12, 19.60, H1b), 2.96 (dd, 1H, J=10.29, 18.9, H1a), 3.90 (s, 3H, CH3O8), 3.95-3.99 (m, 5H, H3b, H11a and CH3O7), 4.21 (d, 1H, J=12.02 Hz, Cl3CCH2), 4.32 (d, 1H, J=20.93 Hz, H3a), 5.24 (d, 1H, J=12.03 Hz, Cl3CCH2), 5.83 (d, 1H, J=9.26 Hz, H11), 6.77 (s, 1H, H9), 7.25 (s, 1H, H6); 13C NMR (CDCl3, 125 MHz) δ 207.8 (C2), 168.0 (C5), 153.7 (OC═ONH), 151.4 (C8), 149.2 (C7), 128.0 (C9-10), 124.5 (C5-6), 113.0 (C9), 110.4 (C6), 95.1 (Cl3C), 87.4 (C11), 74.8 (Cl3CCH2), 58.9 (C11a), 56.2 (CH3O7), 56.0 (CH3O8), 52.8 (C3), 40.3 (C1), 25.5 (C(CH3)3), 17.8 (Cquat), −4.2 and −5.3 (Si(CH3)2); IR (film) 2934, 1763 (C═O), 1720 (OC═ON), 1649 (NC═O), 1604, 1515, 1402, 1274, 1217, 1120, 1075, 1002, 866, 834, 756, 712 cm−1; MS (EI) m/z (relative intensity) 615 ([M+MeOH]+., 100).

후처리

  1. additionthe reaction mixture was diluted with DAM (50 mL)
  2. washThe organic phase was washed
  3. dry with materialdried (MgSO4)
  4. concentrationconcentrated in vacuo
  5. customPurification by flash chromatography (EtOAc/Petroleum ether 6:4)

출처 및 근거

ORD 기록
ord-e4b0550c05b740be88099225c8cb6006
출처 데이터셋
uspto-grants-2010_06
특허 번호
US07741319B2

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