Methyl 2,2-dimethylacetoacetate → Methyl (3R)-3-hydroxy-2,2-dimethylbutanoate

HRID 386896ノート

反応式

HRID 386896 の反応式
[CH3:1][O:2][C:3](=[O:10])[C:4]([CH3:9])([CH3:8])[C:5](=[O:7])[CH3:6]>CO.C1C=CC(P(C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.Cl[Ru]Cl>[CH3:1][O:2][C:3](=[O:10])[C:4]([CH3:9])([CH3:8])[C@H:5]([OH:7])[CH3:6]

参加物

4

反応物 1

HCID 96925Methyl 2,2-dimethylacetoacetate

生成物 1

HCID 12475664Methyl (3R)-3-hydroxy-2,2-dimethylbutanoate収率 95%

試薬・触媒・溶媒 2

HCID 11136527(R)-[2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl dichlororuthenium触媒HCID 887Methanol溶媒

反応条件

温度
30 °C

実験手順

The reaction is carried out in a 100-mL autoclave. 2,2-Dimethyl-3-oxo-butyric acid methyl ester (4.0 g, 27.8 mmol) is dissolved in 35 mL of degassed methanol under Argon atomosphere. Dichloro[(R)-(+)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl]ruthenium (II) (230.0 mg, 0.28 mmol) is added and the reaction mixture is purged with nitrogen twice and once with hydrogen. The autoclave is pressurized with hydrogen to 500 psi and stirred at 30° C. for 40 h. After this time, the reaction mixture is filtered through celite and concentrated under reduced pressure to provide 3.8 g of the title compound as a green oil with ee of 96%. Yield: 95%. 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.15 (3H, d, J=6.4 Hz), 1.2 (6H, d, J=5.2 Hz), 2.6 (1H, br. s), 3.7 (3H, s), 3.9 (1H, q, J=6.4 Hz).

後処理

  1. customthe reaction mixture is purged with nitrogen twice
  2. filtrationAfter this time, the reaction mixture is filtered through celite and
  3. concentrationconcentrated under reduced pressure

出典と根拠

ORDレコード
ord-3c026a91520343239ff5491dacbe8548
出典データセット
uspto-grants-2013_02
特許番号
US08372874B2

反応ノート

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