Methanol → 14-tert-Butoxycarbonylamino-18-(tert-butyldimethylsilanyloxy)-2,15-dioxo-3,16-diaza-tricyclo[14.3.0.04,6]nonadec-7-ene-4-carboxylic acid

HRID 346959

反応式

HRID 346959 の反応式
C([O:3][C:4]([C:6]12[CH2:24][CH:23]1[CH:22]=[CH:21][CH2:20][CH2:19][CH2:18][CH2:17][CH2:16][CH:15]([NH:25][C:26]([O:28][C:29]([CH3:32])([CH3:31])[CH3:30])=[O:27])[C:14](=[O:33])[N:13]1[CH:9]([CH2:10][CH:11]([O:34][Si:35]([C:38]([CH3:41])([CH3:40])[CH3:39])([CH3:37])[CH3:36])[CH2:12]1)[C:8](=[O:42])[NH:7]2)=[O:5])C.C1COCC1.CO.O.[OH-].[Li+]>O>[C:29]([O:28][C:26]([NH:25][CH:15]1[C:14](=[O:33])[N:13]2[CH:9]([CH2:10][CH:11]([O:34][Si:35]([C:38]([CH3:40])([CH3:39])[CH3:41])([CH3:37])[CH3:36])[CH2:12]2)[C:8](=[O:42])[NH:7][C:6]2([C:4]([OH:5])=[O:3])[CH:23]([CH2:24]2)[CH:22]=[CH:21][CH2:20][CH2:19][CH2:18][CH2:17][CH2:16]1)=[O:27])([CH3:30])([CH3:31])[CH3:32]

参加物

6

反応物 4

HCID 887MethanolHCID 8028TetrahydrofuranHCID 168937Lithium hydroxide, monohydrateHCID 6733002714-Tert-butoxycarbonylamino-18-(tert-butyl-dimethyl-silanyloxy)-2,15-dioxo-3,16-diaza-tricyclo[14.3.0.04,6]nonadec-7-ene-4-carboxylic acid ethyl ester

生成物 1

HCID 6732983314-tert-Butoxycarbonylamino-18-(tert-butyldimethylsilanyloxy)-2,15-dioxo-3,16-diaza-tricyclo[14.3.0.04,6]nonadec-7-ene-4-carboxylic acid収率 84%

試薬・触媒・溶媒 1

HCID 962Water溶媒

実験手順

To a solution of 14-tert-butoxycarbonylamino-18-(tert-butyl-dimethyl-silanyloxy)-2,15-dioxo-3,16-diaza-tricyclo[14.3.0.04,6]nonadec-7-ene-4-carboxylic acid ethyl ester (1.5 g, 2.47 mmoL) in a mixed solvent system of THF (4 mL), methanol (1 mL), and water (2 mL), was added powdered lithium hydroxide monohydrate (1.0 g, 50 mmoL). The light yellow slurry was stirred at rt under N2 for 4 h. The mixture was then concentrated in vacuo, and the residue partioned between ether and water. The ether phase was discarded, and the aqueous phase was treated with 1 N HCl until reaching pH 4. This acidic solution was extracted with EtOAc (3×). The combined EtOAc extracts were dried (MgSO4), and concentrated in vacuo to give 1.2 g (84%) of 14-tert-butoxycarbonylamino-18-(tert-butyl-dimethyl-silanyloxy)-2,15-dioxo-3,16-diaza-tricyclo[14.3.0.04,6]nonadec-7-ene-4-carboxylic acid as an off-white solid. 1H NMR (300 MHz, CD3OD) 0.12 (s, 6H), 0.89 (s, 9H), 1.23–1.64 (m, 17H), 1.70–1.87 (m, 1H), 1.90–2.49 (m, 6H), 3.70–3.80 (m, 1H), 3.83–3.90 (m, 1H), 4.28–4.36 (m, 1H), 4.47–4.55 (m, 1H), 4.65 (s, 1H), 5.30–5.39 (m, 1H), 5.53–5.62 (m, 1H). LC-MS (Method A, retention time: 3.69 min), MS m/z 580 (M++1).

後処理

  1. concentrationThe mixture was then concentrated in vacuo
  2. additionthe aqueous phase was treated with 1 N HCl
  3. extractionThis acidic solution was extracted with EtOAc (3×)
  4. dry with materialThe combined EtOAc extracts were dried (MgSO4)
  5. concentrationconcentrated in vacuo

出典と根拠

ORDレコード
ord-a6f42a8963514830923d4095042afeac
出典データセット
uspto-grants-2007_02
特許番号
US07173004B2

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