Dimethyl malonate → dimethyl (R)-2-(1-(4-chlorophenyl)-2-nitroethyl)malonate

Participants

Reaction Conditions

Reaction Steps

This hydrated coarse crystal of 4-chloro-β-nitrostyrene was dissolved in toluene (19 ml), the aqueous phase was separated by a liquid-separation operation, and the organic phase was azeotropically dehydrated under reduced pressure, to distill off 9.5 ml. A catalyst prepared according to a method described in non-patent document 2 (nickel(II)bis[(S,S)—N,N′-dibenzylcyclohexane-1,2-diamine]bromide) (58 mg, 0.072 mmol) and dimethyl malonate (2.3 g, 17 mmol) were added, and the mixture was heated up to 50° C. and stirred at the same temperature for 7 hours. After completion of the reaction, the reaction solution was washed with 0.1 mol/L hydrochloric acid (5 ml) and water (5 ml) each once. The organic phase was concentrated under reduced pressure, and crystallized in a toluene/heptane solvent, to obtain 4.2 g (13 mmol) of a title compound. Yield 75%. The spectrum data corresponded to the value in non-patent document 3. The optical purity of the resultant title compound was measured by HPLC to find a value of 94% ee.

Provenance & Evidence