Imidazole → HCID 58747916、化合物

HRID 1942572ノート

反応式

HRID 1942572 の反応式
[CH2:1]([O:8][C@@H:9]([C@H:12]([C@@H:21]([CH2:23][O:24][CH2:25][C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1)[OH:22])[O:13][CH2:14][C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1)[CH2:10][OH:11])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.N1C=CN=C1.[CH3:37][C:38]([Si:41](Cl)([CH3:43])[CH3:42])([CH3:40])[CH3:39]>CN(C=O)C>[CH2:1]([O:8][C@@H:9]([C@H:12]([C@@H:21]([CH2:23][O:24][CH2:25][C:26]1[CH:27]=[CH:28][CH:29]=[CH:30][CH:31]=1)[OH:22])[O:13][CH2:14][C:15]1[CH:16]=[CH:17][CH:18]=[CH:19][CH:20]=1)[CH2:10][O:11][Si:41]([C:38]([CH3:40])([CH3:39])[CH3:37])([CH3:43])[CH3:42])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

参加物

5

反応物 3

HCID 795ImidazoleHCID 28928tert-Butyldimethylsilyl chlorideHCID 58747826HCID 58747826、化合物

生成物 1

HCID 58747916HCID 58747916、化合物収率 93%

試薬・触媒・溶媒 1

HCID 6228Dimethylformamide溶媒

反応条件

温度
0 °C

実験手順

A mixture of 239 (5.24 g, 12.4 mmol), imidazole (3.72 g, 54.6 mmol), and TBDMSCl (2.07 g, 13.6 mmol) in dry DMF (50 mL) was stirred at 0° C. under N2 for 30 min. The reaction was quenched with ice (20 mL), and the reaction mixture was partitioned between Et2O (200 mL) and H2O (100 mL). The separated organic phase was washed with H2O (100 mL) and brine (100 mL). The organic layer was dried over anhydrous Na2SO4 and concentrated. The residue was purified by flash chromatography (hexanes:EtOAc, 3:1) to give a colorless oil 240 (6.164 g, 93%): [α]D −140.4° (c 0.87, CHCl3); 1H NMR (CDCl3) δ 7.35-7.25 (15H, m, Ar), 4.74 and 4.60 (2H, 2d, Ja,b=11.7 Hz, CH2Ph), 4.69 and 4.51 (2H, 2d, Ja,b=11.9 Hz, CH2Ph), 4.51 and 4.45 (2H, 2d, Ja,b=11.6 Hz, CH2Ph), 4.05 (1H, dddd, J3,4=2.3 Hz, J4,5a=J4,5b=5.9 H,J4,OH=5.9 Hz, H-4), 3.88 (1H, dd, J1a,1b=11.0 Hz, J1a,2=4.2 Hz, H-1a), 3.78 (1H, dd, J1b,2=4.9 Hz, H-1b), 3.77 (1H, dd, J2,3=4.1 Hz, H-3), 3.73 (1H, ddd, H-2), 3.54(1H, dd, H-5a), 3.49 (1H, dd, H-5b), 3.02 (1H, d, OH), 0.891 (9H, s, (CH3)3CSi), 0.05 (6H, s, (CH3)2Si); 13C NMR (CDCl3) δ 149.11, 145.62, 140.95 (3Cipso), 128.35-127.60 (15C, Ar), 80.25 (C-2), 77.25 (C-3), 73.65, 73.26, 72.84 (3CH2Ph), 71.16 (C-5), 69.75 (C-4), 62.04 (C-1), 25.88 (3C, (CH3)3CSi) 18.23 (1C, CSi), −5.40, −5.44 (2C, (CH3)2Si); MALDI-TOF MS: m/e 537.89 (M++H), 559.33 (M++Na). Anal. Calcd for C32H44O5Si: C, 71.60; H, 8.26. Found: C, 71.44; H, 8.34.

後処理

  1. customThe reaction was quenched with ice (20 mL)
  2. customthe reaction mixture was partitioned between Et2O (200 mL) and H2O (100 mL)
  3. washThe separated organic phase was washed with H2O (100 mL) and brine (100 mL)
  4. dry with materialThe organic layer was dried over anhydrous Na2SO4
  5. concentrationconcentrated
  6. customThe residue was purified by flash chromatography (hexanes:EtOAc, 3:1)

出典と根拠

ORDレコード
ord-9b24d2181d3b43a6ad5ca06ec10f7363
出典データセット
uspto-grants-2013_03
特許番号
US08389565B2

反応ノート

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