(2S,4R)-1-allyloxycarbonyl-4-hydroxy-2-hydroxymethylpyrrolidine → (11aS)-7-Iodo-2-methylidene-1,2,3,11a-tetrahydro-5H-pyrrolo[2,1-c][1,4]benzodiazepin-5-one

HRID 915702노트

반응식

HRID 915702 반응식
C(OC(N1C[C@H](O)C[C@H]1CO[Si](C(C)(C)C)(C)C)=O)C=C.C(OC(N1C[C@H](O)C[C@H]1CO)=O)C=C.O[C@H:37]1[C@@H:43]2[CH2:44][C:45](=[CH2:47])[CH2:46][N:42]2[C:41](=[O:48])[C:40]2[CH:49]=[C:50]([I:53])[CH:51]=[CH:52][C:39]=2[N:38]1NC(OCC(Cl)(Cl)Cl)=O.[Si](OC[C@@H]1CC(=C)CN1)(C(C)(C)C)(C)C>>[I:53][C:50]1[CH:51]=[CH:52][C:39]2[N:38]=[CH:37][C@@H:43]3[CH2:44][C:45](=[CH2:47])[CH2:46][N:42]3[C:41](=[O:48])[C:40]=2[CH:49]=1

참가 물질

5

반응물 4

HCID 15086219(2S,4R)-1-allyloxycarbonyl-4-hydroxy-2-hydroxymethylpyrrolidine8회HCID 18639173(2S,4R)-1-allyloxycarbonyl-2-t-butyldimethylsilyloxymethyl-4-hydroxypyrrolidine6회HCID 58400350(2S)-2-[[[(1,1-Dimethylethyl)dimethylsilyl]oxy]methyl]-4-methylenepyrrolidine2회HCID 69462904(11S,11aS)-11-Hydroxy-7-iodo-2-methylidene-10-(2,2,2-trichloroethyloxycarbonylamino)-1,2,3,10,11,11a-hexahydro-5H-pyrrolo[2,1-c][1,4]benzodiazepin-5-one

생성물 1

HCID 9862665(11aS)-7-Iodo-2-methylidene-1,2,3,11a-tetrahydro-5H-pyrrolo[2,1-c][1,4]benzodiazepin-5-one

실험 절차

10% cadmium-lead couple (109 mg, 0.875 mmol) was added to a stirred solution of the Troc-protected carbinolamine 13 (93 mg, 0.175 mmol) in THF (1 mL) and aqueous 1 N ammonium acetate (1 mL). After 45 minutes at room temperature TLC revealed complete reaction (70% EtOAc/Petroleum Ether). The mixture was diluted with EtOAc (30 mL), dried (MgSO4), filtered and evaporated in vacuo. The crude residue was purified by flash chromatography (70% EtOAc/Petroleum Ether) to provide the novel PBD (14, BSD-SJG, UP2023) as a white solid (27 mg, 46%): mp ° C.; 1H NMR (270 MHz, CDCl3+CD3OD) (11S,11aS isomer) δ 8.10 (d, 1H, J=1.46Hz), 7.65 (d, 1H, J=8.79 Hz), 6.86 (d, 1H, J=8.06 Hz), 5.14-5.10 (m, 2H), 4.66 (d, 1H, J=5.13 Hz), 4.34 (d, 1H, J=16.12 Hz), 4.23 (d, 1H, J=16.12 Hz), 3.80-3.71 (m, 1H), 3.34 (s, 3H), 3.03-2.86 (m, 1H), 2.65 (d, 1H, J=16.02 Hz); MS (EI), m/z (relative intensity) (N10-C11 imine form) 339 (M++1, 20), 338 (M+, 100), 337 (17), 323 (5), 311 (4), 310 (5), 257 (5), 230 (4), 229 (13), 211 (4), 203 (4), 202 (8), 184 (8), 183 (4), 103 (5), 82 (17), 81 (4), 80 (5), 76 (6), 75 (16), 74 (5), 55 (4), 53 (4); IR (NUJOL7) 3295 (br), 2923, 2853, 1716, 1615, 1506, 1457, 1377, 1317, 1278, 1238, 1169, 1118, 1063, 999, 895, 818, 751, 718 cm−1; exact mass calcd for C13H11N2OI m/e 337.9916, obsd m/e 337.9870.

출처 및 근거

ORD 기록
ord-3e4596c16c254c0d9b06844ed508f540
출처 데이터셋
uspto-grants-2007_09
특허 번호
US07265105B2

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