Diethyl allylmalonate

The malonic ester required for synthesis of cyclopal (107) can be obtained by alkylation of diethyl allylmalonate (115) with 1,2-dibromocyclopentane in the presence of excess base. It is probable that the reaction proceeds by elimination of hydrogen bromide from the dihalide as the first step. The resulting allilic halide (116) would be the most reactive electrophile in the reaction mixture and thus would quickly alkylate the anion of the malonate to afford 117. 

Diethyl 1,1-cyclobutanedicarboxylate has been prepared by the alkylation of diethyl sodiomalonate with trimethylene dibromide 8i4>6 7 or with trimethylene chlorobromide 6-8 and by the peroxide-catalyzed addition of hydrogen bromide to diethyl allylmalonate followed by intramolecular alkylation.9 The procedure described here is that of Mariella and Raube.6... 

Ortho ester Claisen rearrangement.2 The [3,3]sigmatropic rearrangement of allyl vinyl alcohols prepared from this ester results in a regiospecific synthesis of diethyl allylmalonates. 

Charge the second flame dried and argon flushed two-necked flask with diethyl allylmalonate and cool to 0°C. 

Slowly add diethylborane to the diethyl allylmalonate. Allow to warm to rt and stir for 3 h. 

Prepared by reaction of diethyl sodioallylmalonate, from diethyl allylmalonate (l.OA/) and NaH in THF, and 2,3-dibromoprop-l-ene, aqueous work-up and flash chromatography. 

In 2005, Azim, Sahoo, and Gross [47] reported the use of immobilized lipase B from Candida antarctica (Novozym 435) as a catalyst for direct formation of amide bonds between dialkyl esters and diamines under mild reaction conditions. Oligoamides were obtained with DP up to 9. The example of the reaction of diethyl allylmalonate and 1,12-dodecanediamine is shown in Scheme 5.2, and the oligoamide structure elucidated by H NMR. 

Dicyclonexylnonane Diethanolacetylene Diethyl acetaldehyde Diethylal lylacetophenone Diethyl allylmalonate Diethvlamine Diethylcyclohexylamine Diethjl ethylmalonate Diethyl ketone Diethyl ketoxime Diethyl malonate Diethyl-3-(l-methyl butane) ethyl... 

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