Sodium Bicarbonate → Methyl 3-{2-[(acetyloxy)methyl]-4-[(tert-butoxycarbonyl)amino]-3-methylphenyl}-2-{[(benzyloxy)carbonyl]amino}prop-2-enoate

HRID 132289

反応式

HRID 132289 の反応式
[C:1]([O:5][C:6]([NH:8][C:9]1[C:10]([CH3:21])=[C:11]([C:17](I)=[CH:18][CH:19]=1)[CH2:12][O:13][C:14](=[O:16])[CH3:15])=[O:7])([CH3:4])([CH3:3])[CH3:2].[CH3:22][O:23][C:24]([C:26]([NH:28][C:29]([O:31][CH2:32][C:33]1[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1)=[O:30])=[CH2:27])=[O:25].C(=O)(O)[O-].[Na+]>O.[Cl-].C([N+](CCCC)(CCCC)CCCC)CCC.C1COCC1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH3:22][O:23][C:24](=[O:25])[C:26]([NH:28][C:29]([O:31][CH2:32][C:33]1[CH:34]=[CH:35][CH:36]=[CH:37][CH:38]=1)=[O:30])=[CH:27][C:17]1[CH:18]=[CH:19][C:9]([NH:8][C:6]([O:5][C:1]([CH3:4])([CH3:3])[CH3:2])=[O:7])=[C:10]([CH3:21])[C:11]=1[CH2:12][O:13][C:14](=[O:16])[CH3:15]

参加物

7

反応物 3

HCID 516892Sodium BicarbonateHCID 3525700Z-Dehydro-Ala-OMeHCID 534147073-(Tert-butoxycarbonylamino)-6-iodo-2-methylbenzyl acetate

生成物 1

HCID 53415138Methyl 3-{2-[(acetyloxy)methyl]-4-[(tert-butoxycarbonyl)amino]-3-methylphenyl}-2-{[(benzyloxy)carbonyl]amino}prop-2-enoate収率 69%

試薬・触媒・溶媒 3

HCID 167845palladium(II) acetate触媒HCID 16212273Tetrabutylammonium chloride hydrate触媒HCID 8028Tetrahydrofuran溶媒

実験手順

Palladium (II) acetate (105 mg, 0.43 mmol) was added to a mixture of acetic acid 3-tert-butoxycarbonylamino-6-iodo-2-methyl-benzyl ester (2.89 g, 7.1 mmol), Z-dehydroalanine methyl ester (2.20 g, 9.4 mmol), tetrabutylammonium chloride hydrate (2.70 g, 9.7 mmol), and sodium bicarbonate (1.80 g, 21.4 mmol) in THF (100 mL). Reaction was heated at reflux for 3.75 hours. Mixture was cooled to room temperature then filtered through a plug of silica gel eluting 70% ethyl acetate-hexanes (500 mL). Filtrate was concentrated in vacuo. Silica gel chromatography afforded the title compound as a yellow solid in 69% yield. 1H NMR (300 MHz, CDCl3): δ=7.79 (d, J=8.4, 1H), 7.42 (s, 1H), 7.27 (m, 6H), 6.30 (s, 1H), 5.11 (s, 2H), 5.02 (s, 2H), 3.81 (s, 3H), 2.21 (s, 3H), 2.02 (s, 3H), 1.51 (s, 9H). MS m/e (M−H)−=511.0.

後処理

  1. customReaction
  2. temperaturewas heated
  3. temperatureat reflux for 3.75 hours
  4. filtrationthen filtered through a plug of silica gel eluting 70% ethyl acetate-hexanes (500 mL)
  5. concentrationFiltrate was concentrated in vacuo

出典と根拠

ORDレコード
ord-439f2396daaf45e8a85daf34b08fefa2
出典データセット
uspto-grants-2008_06
特許番号
US07384931B2

関連ノート

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