Acetic Acid → Benzyl ((2S,3R)-1-(4-((tert-butyloxycarbonylamino)methyl)phenyl)-3-hydroxy-4-methylpent-4-en-2-yl)carbamate

HRID 1253411ノート

反応式

HRID 1253411 の反応式
[C:1]([O:5][C:6]([NH:8][CH2:9][C:10]1[CH:15]=[CH:14][C:13]([CH2:16][C@H:17]([NH:23][C:24](=[O:33])[O:25][CH2:26][C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)[C:18](=[O:22])[C:19]([CH3:21])=[CH2:20])=[CH:12][CH:11]=1)=[O:7])([CH3:4])([CH3:3])[CH3:2].[BH4-].[Na+].C(O)(=O)C>CO>[CH2:26]([O:25][C:24](=[O:33])[NH:23][C@H:17]([C@H:18]([OH:22])[C:19]([CH3:21])=[CH2:20])[CH2:16][C:13]1[CH:12]=[CH:11][C:10]([CH2:9][NH:8][C:6]([O:5][C:1]([CH3:4])([CH3:2])[CH3:3])=[O:7])=[CH:15][CH:14]=1)[C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1

参加物

5

反応物 3

HCID 176Acetic AcidHCID 4311764Sodium borohydrideHCID 71562123(S)-Benzyl (1-(4-((tert-butyloxycarbonylamino)methyl)phenyl)-4-methyl-3-oxopent-4-en-2-yl)carbamate

生成物 1

HCID 71562124Benzyl ((2S,3R)-1-(4-((tert-butyloxycarbonylamino)methyl)phenyl)-3-hydroxy-4-methylpent-4-en-2-yl)carbamate

試薬・触媒・溶媒 1

HCID 887Methanol溶媒

反応条件

温度
0 °C

実験手順

Ketone 12 (2.81 g, 4.30 mmol) was dissolved in MeOH (25 mL) and cooled to 0° C. To this were added CeCl3.7H2O (1.5 eq., 6.45 mmol, 2.43 g) and NaBH4 (1.4 eq., 6.0 mmol, 227 mg) portion-wise and the mixture was stirred for 5 minutes. after which TLC analysis indicated a complete conversion. Glacial acetic acid (10 mL) was added and the mixture was concentrated under reduced pressure. The resulting residue was dissolved in EtOAc and extracted with half saturated aq. NaHCO3 (2×) and brine, dried over MgSO4 and concentrated in vacuo. The title compound was obtained as a colourless oil (yield: 1.79 g, 3.94 mmol, 92%). 1H NMR (400 MHz, CDCl3): δ=7.31-7.01 (m, 9H), 5.30 (d, J=9.18 Hz, 1H), 5.06 (s, 1H), 5.00 (d, J=5.19 Hz, 1H), 4.96-4.91 (m, 3H), 4.21 (d, J=4.41 Hz, 1H), 4.16-4.11 (m, 1H), 4.07-3.98 (m, 1H), 2.85 (d, J=12.55 Hz, 1H), 2.65 (dd, J=13.60, 10.41 Hz, 1H), 1.77 (s, 3H), 1.44 (s, 9H) ppm. 13C NMR (100 MHz, CDCl3): δ=155.96, 155.85, 144.44, 137.34, 136.44, 129.34, 128.19, 127.77, 127.66, 127.25, 112.17, 79.25, 76.65, 66.27, 54.06, 44.15, 33.69, 28.22, 18.73 ppm. [α]D23=−18.7 (c=1, CHCl3). HRMS: calcd. for C26H34N2O5 455.25405 [M+H]+. Found 455.25392.

後処理

  1. concentrationthe mixture was concentrated under reduced pressure
  2. dissolutionThe resulting residue was dissolved in EtOAc
  3. extractionextracted with half saturated aq. NaHCO3 (2×) and brine
  4. dry with materialdried over MgSO4
  5. concentrationconcentrated in vacuo

出典と根拠

ORDレコード
ord-e0da8ecda5904b38b69d184200f251bd
出典データセット
uspto-grants-2013_06
特許番号
US08455431B2

反応ノート

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