(Triphenylphosphoranylidene)acetonitrile → ((R)-3-cyano-1-methyl-allyl)-carbamic acid tert-butyl ester

HRID 246215

反応式

HRID 246215 の反応式
[C:1]([O:5][C:6](=[O:12])[NH:7][C@H:8]([CH3:11])[CH:9]=O)([CH3:4])([CH3:3])[CH3:2].C1(P(=[CH:32][C:33]#[N:34])(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>ClCCl>[C:1]([O:5][C:6](=[O:12])[NH:7][C@H:8]([CH3:11])[CH:9]=[CH:32][C:33]#[N:34])([CH3:4])([CH3:3])[CH3:2]

参加物

4

反応物 2

HCID 85524(Triphenylphosphoranylidene)acetonitrileHCID 10910049tert-butyl N-((2R)-1-oxopropan-2-yl)carbamate

生成物 1

HCID 86677956((R)-3-cyano-1-methyl-allyl)-carbamic acid tert-butyl ester収率 63.7%

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒

実験手順

In a 20 mL scintillation vial, ((R)-1-methyl-2-oxo-ethyl)-carbamic acid tert-butyl ester (2.5 g, 14.4 mmol) and (triphenylphosphoranylidene)acetonitrile (6.52 g, 21.7 mmol) were mixed in dichloromethane (20 mL) and stirred at room temperature for 16 h. The solvent was evaporated to give the crude material, which was purified by column chromatography (silica gel, gradient n-hexanes ethyl acetate) to provide 1.8 g (63%) of ((R)-3-cyano-1-methyl-allyl)-carbamic acid tert-butyl ester in a 3:1 diastereoselectivity (E:Z) as a colorless oil. 1H NMR (300 MHz, CDCl3) δ ppm 6.38-6.79 (m, 1H), 5.47 (dd, J=16.24, 1.89 Hz, 1H), 4.48 (bs, 1H), 4.47 (bs, 1H), 1.45 (s, 1H), 1.28 (d, J=7.18 Hz, 9H).

後処理

  1. customThe solvent was evaporated
  2. customto give the crude material, which
  3. customwas purified by column chromatography (silica gel, gradient n-hexanes ethyl acetate)

出典と根拠

ORDレコード
ord-fc346cea310b4a4e9983a907bd66bedf
出典データセット
uspto-grants-2014_02
特許番号
US08658646B2

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