(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 915702ノート

反応式

HRID 915702 の反応式
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

参加物

5

反応物 4

HCID 15086219(2S,4R)-1-allyloxycarbonyl-4-hydroxy-2-hydroxymethylpyrrolidine8 回HCID 18639173(2S,4R)-1-allyloxycarbonyl-2-t-butyldimethylsilyloxymethyl-4-hydroxypyrrolidine6 回HCID 58400350(2S)-2-[[[(1,1-Dimethylethyl)dimethylsilyl]oxy]methyl]-4-methylenepyrrolidine2 回HCID 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

生成物 1

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

実験手順

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.

出典と根拠

ORDレコード
ord-3e4596c16c254c0d9b06844ed508f540
出典データセット
uspto-grants-2007_09
特許番号
US07265105B2

反応ノート

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