Boron trifluoride etherate → Benzyl 8-ethyl-7-((3aR,4R,7R,7aR)-7-methoxy-6,6-dimethyl-2-oxotetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-4-yloxy)-2-oxo-2H-chromen-3-ylcarbamate

HRID 1511236ノート

反応式

HRID 1511236 の反応式
B(F)(F)F.CCOCC.[CH2:10]([C:12]1[C:13]([OH:34])=[CH:14][CH:15]=[C:16]2[C:21]=1[O:20][C:19](=[O:22])[C:18]([NH:23][C:24](=[O:33])[O:25][CH2:26][C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1)=[CH:17]2)[CH3:11].ClC(Cl)(Cl)C(=N)O[C@H:39]1[C@@H:44]2[O:45][C:46](=[O:48])[O:47][C@@H:43]2[C@@H:42]([O:49][CH3:50])[C:41]([CH3:52])([CH3:51])[O:40]1.C(N(CC)CC)C>C(Cl)Cl>[CH2:10]([C:12]1[C:13]([O:34][C@H:39]2[C@@H:44]3[O:45][C:46](=[O:48])[O:47][C@@H:43]3[C@@H:42]([O:49][CH3:50])[C:41]([CH3:52])([CH3:51])[O:40]2)=[CH:14][CH:15]=[C:16]2[C:21]=1[O:20][C:19](=[O:22])[C:18]([NH:23][C:24](=[O:33])[O:25][CH2:26][C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1)=[CH:17]2)[CH3:11]

参加物

6

反応物 4

HCID 8000Boron trifluoride etherateHCID 8471TriethylamineHCID 25138792Benzyl 8-ethyl-7-hydroxy-2-oxo-2H-chromen-3-ylcarbamateHCID 67094064(3aR,4S,7R,7aR)-7-methoxy-6,6-dimethyl-2-oxo-tetrahydro-3aH-[1.3]dioxolo[4,5-c]pyran-4-yl 2,2,2-trichloroacetimidate

生成物 1

HCID 25140543Benzyl 8-ethyl-7-((3aR,4R,7R,7aR)-7-methoxy-6,6-dimethyl-2-oxotetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-4-yloxy)-2-oxo-2H-chromen-3-ylcarbamate収率 51%

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒

実験手順

Boron trifluoride etherate (19.0 μL, 0.15 mmol) was added to 23h (171 mg, 0.51 mmol) and (3aR,4S,7R,7aR)-7-methoxy-6,6-dimethyl-2-oxo-tetrahydro-3aH-[1.3]dioxolo[4,5-c]pyran-4-yl 2,2,2-trichloroacetimidate (183 mg, 0.51 mmol) in anhydrous CH2Cl2 (11.0 mL). After stirring at room temperature for 24 hours, triethylamine (150 μL) was added and the solvent was concentrated. The residue was purified via column chromatography (SiO2, 40:1 CH2Cl2:Acetone) to give 25h as a colorless foam (138 mg, 51%): 1H NMR (CD2Cl2, 400 MHz) 8.29 (s, 1H), 7.62 (s, 1H), 7.47-7.38 (m, 5H), 7.36 (d, J=8.8 Hz, 1H), 7.19 (d, J=8.4 Hz, 1H), 5.81 (d, J=2.4 Hz, 1H), 5.25 (s, 2H), 5.10 (dd, J=8.0, 2.0 Hz, 1H), 5.02 (t, J=7.8 Hz, 1H), 3.55 (s, 3H), 3.41 (d, J=7.2 Hz, 1H), 2.87 (q, J=7.4 Hz, 2H), 1.42 (s, 3H), 1.28 (s, 3H), 1.21 (t, J=7.4 Hz, 3H); 13C NMR (CD2Cl2, 100 MHz) 158.5, 154.8, 153.2, 153.1, 148.4, 136.0, 128.6 (2C), 128.4, 128.1, 125.6, 122.4, 121.5, 120.7, 114.8, 111.4, 94.8, 82.7, 77.9, 77.2, 76.6, 67.3, 60.3, 27.3, 22.3, 16.4, 13.6; IR (film) νmax 3400, 2980, 2937, 2359, 2339, 1817, 1711, 1607, 1524, 1383, 1366, 1227, 1205, 1175, 1101, 1040, 906, 768, 737, 700 cm−1; [M+Na]+ calcd for C28H29NO10, 562.1689. found, 562.1689.

後処理

  1. concentrationthe solvent was concentrated
  2. customThe residue was purified via column chromatography (SiO2, 40:1 CH2Cl2:Acetone)

出典と根拠

ORDレコード
ord-d4255eb5eba44037b7a6962b65163b22
出典データセット
uspto-grants-2012_07
特許番号
US08212011B2

反応ノート

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