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

反応式

HRID 18866 の反応式
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

参加物

5

反応物 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

生成物 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

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒

実験手順

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).

後処理

  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)

出典と根拠

ORDレコード
ord-e4b0550c05b740be88099225c8cb6006
出典データセット
uspto-grants-2010_06
特許番号
US07741319B2

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