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(S,E)-(2-((tert-butyldimethylsilyloxy)methyl)-4-(prop-1-enyl)-2,3-dihydro-1H-pyrrol-1-yl)(5-methoxy-2-nitro-4-(triisopropylsilyloxy)phenyl)methanone → (S,E)-(2-amino-5-methoxy-4-(triisopropylsilyloxy)phenyl)(2-((tert-butyldimethylsilyloxy)methyl)-4-(prop-1-enyl)-2,3-dihydro-1H-pyrrol-1-yl)methanone

HRID 513358
ノート
印刷プレビュー

反応式

HRID 513358 の反応式
[Si:1]([O:8][CH2:9][C@@H:10]1[CH2:14][C:13](/[CH:15]=[CH:16]/[CH3:17])=[CH:12][N:11]1[C:18]([C:20]1[CH:25]=[C:24]([O:26][CH3:27])[C:23]([O:28][Si:29]([CH:36]([CH3:38])[CH3:37])([CH:33]([CH3:35])[CH3:34])[CH:30]([CH3:32])[CH3:31])=[CH:22][C:21]=1[N+:39]([O-])=O)=[O:19])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2]>[Zn].C(O)=O.C(O)C>[NH2:39][C:21]1[CH:22]=[C:23]([O:28][Si:29]([CH:33]([CH3:34])[CH3:35])([CH:36]([CH3:38])[CH3:37])[CH:30]([CH3:32])[CH3:31])[C:24]([O:26][CH3:27])=[CH:25][C:20]=1[C:18]([N:11]1[CH:12]=[C:13](/[CH:15]=[CH:16]/[CH3:17])[CH2:14][C@H:10]1[CH2:9][O:8][Si:1]([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:2])[CH3:3])=[O:19]
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

4

反応物 1

HCID 86717761(S,E)-(2-((tert-butyldimethylsilyloxy)methyl)-4-(prop-1-enyl)-2,3-dihydro-1H-pyrrol-1-yl)(5-methoxy-2-nitro-4-(triisopropylsilyloxy)phenyl)methanone

生成物 1

HCID 86717762(S,E)-(2-amino-5-methoxy-4-(triisopropylsilyloxy)phenyl)(2-((tert-butyldimethylsilyloxy)methyl)-4-(prop-1-enyl)-2,3-dihydro-1H-pyrrol-1-yl)methanone収率 69%

試薬・触媒・溶媒 2

HCID 23994Zinc触媒HCID 23437341
Formic acid ethanol
溶媒

反応条件

温度
27.5 °C

実験手順

Zinc dust (22.0 g, 0.33 mol, 37 eq) was added, in portions over 20 mins, to a solution of the propenyl intermediate 6 (5.5 g, 9.1 mmol, 1.0 eq) in 5% v/v formic acid/ethanol (55 mL), using an ice bath to maintain the temperature between 25-30° C. After 30 mins, the reaction mixture was filtered through a short bed of Celite®. The Celite® was washed with ethyl acetate (65 mL) and the combined organics were washed successively with water (35 mL), saturated sodium bicarbonate (35 mL) and brine (10 mL). The organic phase was dried over MgSO4, filtered and concentrated under reduced pressure. The residue was purified by flash chromatography (silica gel, 90/10 v/v n-hexane/EtOAc) to afford the product as a pale yellow oil (3.6 g, 69.0%). LC/MS (4.439 min (ES+)), m/z: 575.2 [M+H]+. 1H NMR (400 MHz, CDCl3) δ 6.75 (m, 1H), 6.40 (br s, 1H), 6.28 (m, 1H), 6.11 (d, 1H, J=15.4 Hz), 5.53 (m, 1H), 4.67 (m, 1H), 4.36 (m, 2H), 3.93 (br s, 1H), 3.84 (br s, 1H), 3.73 (s, 3H), 2.86 (dd, 1H, J=15.7, 10.4 Hz), 2.73 (dd, 1H, J=15.9, 4.5 Hz), 1.80 (dd, 3H, J=6.8, 1.3 Hz), 1.35-1.23 (m, 3H), 1.12 (d, 18H, J=7.3 Hz), 0.89 (s, 9H), 0.08 (s, 3H), 0.07 (s, 3H).

後処理

  1. filtrationthe reaction mixture was filtered through a short bed of Celite®
  2. washThe Celite® was washed with ethyl acetate (65 mL)
  3. washthe combined organics were washed successively with water (35 mL), saturated sodium bicarbonate (35 mL) and brine (10 mL)
  4. dry with materialThe organic phase was dried over MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. customThe residue was purified by flash chromatography (silica gel, 90/10 v/v n-hexane/EtOAc)

出典と根拠

ORDレコード
ord-41e6412a56984bbcb2e65398b6d6a882
出典データセット
uspto-grants-2015_08
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US09102704B2

反応ノート

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このページの内容参加物反応条件実験手順後処理出典と根拠反応ノート