Water → Dimethyl 2-(1-phenyl-allyl)-malonate

Temperature

60 °C

Cycloheptyl ligand IV (10.2 mg, 0.030 mmol) and Mo(CO)3(EtCN)3 (6.9 mg, 0.020 mmol) were dissolved in 1.0 ml of THF at rt. The reaction mixture was heated at 60° C. for 1 h. After cooling to rt, 1.0 ml of THF solution of sodium dimethylmalonate enolate, prepared from dimethyl malonate (58.0 mg, 0.44 mmol) and sodium hydride (10.2 mg, 0.40 mmol) in tetrahydrofuran, and methyl 3-phenyl-2-propenyl carbonate were added successively. The reaction mixture was heated at 65° C. for 8 h. The reaction mixture was poured into water and extracted with ethyl acetate. The combined organic layers were dried over sodium sulfate, and the solvent was removed under reduced pressure. The ratio of 1,1-dimethoxycarbonyl-2-phenyl-3-butene and linear compound was determined by 1H NMR (400 MHz) to be 34.2/1. The residue was chromatographed on silica (1/8 ethyl acetate/petroleum ether, Rf=0.3) to yield the mixture of branched and linear compound (36.7 mg, 74%). [α]D=−29.7° (c 1.27, CHCl3); 99% ee.

1. temperatureAfter cooling to rt
2. additionwere added successively
3. temperatureThe reaction mixture was heated at 65° C. for 8 h
4. extractionextracted with ethyl acetate
5. dry with materialThe combined organic layers were dried over sodium sulfate
6. customthe solvent was removed under reduced pressure
7. customThe residue was chromatographed on silica (1/8 ethyl acetate/petroleum ether, Rf=0.3)
8. customto yield

ORD record

ord-b9cb2151a0c842aba1338c795a187e51

Source dataset

uspto-grants-2004_06

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US06747152B2