In its diester form dihydroxyfumaric acid (DHF), for the last several decades have been used exclusively has electrophiles to add highly oxidized carbons to nucleophiles. This comes from reactivity with the unsaturated ester portion of the molecule; however, the ene-diol moiety has been underexplored. Recently, decarboxylative nucleophilic reactivity toward aldehydes has been achieved using the DHF acid with basic conditions but it has been limited to aqueous conditions or requiring brucine and cesium carbonate. Herein, we present an improvement on the current organic methods by utilizing only amine bases to achieve cleaner decarboxylation in higher yields. Also, upon changing bases an alternate deoxalation pathway previously only seen in aqueous conditions is shown in organic solvent. Computation and experimental studies were performed on DHF as well as the dicarboxylate and dimethyl ester to determine why the dicarboxylate is necessary for nucleophilic reactivity while the diester reacts as an electrophile. This systematic study of the intrinsic reactivity of DHF will allow for its diverse reaction pathways to be better utilized in the future.

Base dependent chemo-divergent cascade reaction of dihydroxyfumarate with aldehydes

254th National Meeting (2017)

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