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

HRID 386896Notes

Reaction equation

[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]

Participants

Conditions

Temperature: 30 °C

Procedure

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).

Workup

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

Sources & evidence

ORD record: ord-3c026a91520343239ff5491dacbe8548
Source dataset: uspto-grants-2013_02
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08372874B2

Reaction notes

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