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(S)-4-((tert-Butyldimethylsilyl)oxy)butan-2-ol → (S)-4-(tert-butyldimethylsilyloxy)butan-2-yl 2-methoxy-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenylcarbamate

HRID 245717
ノート
印刷プレビュー

反応式

HRID 245717 の反応式
[Si:1]([O:8][CH2:9][CH2:10][C@@H:11]([OH:13])[CH3:12])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].[N:14]([C:17]1[CH:22]=[CH:21][C:20]([B:23]2[O:27][C:26]([CH3:29])([CH3:28])[C:25]([CH3:31])([CH3:30])[O:24]2)=[CH:19][C:18]=1[O:32][CH3:33])=[C:15]=[O:16]>ClCCl.CN(C)C1C=CN=CC=1>[CH3:33][O:32][C:18]1[CH:19]=[C:20]([B:23]2[O:27][C:26]([CH3:28])([CH3:29])[C:25]([CH3:30])([CH3:31])[O:24]2)[CH:21]=[CH:22][C:17]=1[NH:14][C:15](=[O:16])[O:13][C@H:11]([CH2:10][CH2:9][O:8][Si:1]([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2])[CH3:12]
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

5

反応物 2

HCID 10998136(S)-4-((tert-Butyldimethylsilyl)oxy)butan-2-olHCID 866746582-(4-Isocyanato-3-methoxyphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

生成物 1

HCID 67365296(S)-4-(tert-butyldimethylsilyloxy)butan-2-yl 2-methoxy-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenylcarbamate収率 67.2%

試薬・触媒・溶媒 2

HCID 142844-(Dimethylamino)pyridine触媒
HCID 6344
Dichloromethane
溶媒

反応条件

温度
40 °C

実験手順

To (S)-4-(tert-butyldimethylsilyloxy)butan-2-ol (1.649 mmol, 337 mg) in dichloromethane (4 ml) were added mol sieves (4A), 2-(4-isocyanato-3-methoxyphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1.374 mmol, 378 mg) and 4-dimethylaminopyridine (0.275 mmol, 33.6 mg) were added and the mixture was stirred at 40° C. (oil bath temperature) for 18 hours. The mol sieves were removed by filtration and the filtrate washed with water, dried (sodium sulfate) and concentrated in vacuo to give a crude product which was purified by column chromatography (silica gel, heptanes with gradient 10% to 50% of ethyl acetate) to afford (S)-4-(tert-butyldimethylsilyloxy)butan-2-yl 2-methoxy-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenylcarbamate (443 mg). Tetrabutylammonium fluoride (1M in tetrahydrofuran, 1.22 mmol, 1.22 ml) was added to (S)-4-(tert-butyldimethylsilyloxy)butan-2-yl 2-methoxy-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenylcarbamate (240 mg) in tetrahydrofuran (1 ml) at room temperature. After 20 hours water was added to the reaction mixture, extracted with dichloromethane, the organic extract dried (sodium sulfate) and concentration in vacuo to yield (S)-4-hydroxybutan-2-yl 2-methoxy-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenylcarbamate (268 mg) which was used in the next step without further purification.

後処理

  1. additionwere added
  2. customThe mol sieves were removed by filtration
  3. washthe filtrate washed with water
  4. dry with materialdried (sodium sulfate)
  5. concentrationconcentrated in vacuo
  6. customto give a crude product which
  7. customwas purified by column chromatography (silica gel, heptanes with gradient 10% to 50% of ethyl acetate)

出典と根拠

ORDレコード
ord-740425fee6084b7791f0fbed821e3491
出典データセット
uspto-grants-2014_02
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US08658794B2

反応ノート

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