The epimetallation and carbonation of carbonyl and imino derivatives: Epivanadation route to 2-amino and 2-hydroxy acids

The feasibility of hydrocarboxylating carbonyl and imino derivatives by the two-step process of epimetallation and carbonation has been demonstrated with the model substrates of 9-fluorenone and 9-fluorenone anil. With lithium vanadium dihydride as the epimetallating agent, such hydrocarboxylation has led to a 75% yield of 9-hydroxy-9-fluorenecarboxylic acid and a 65% yield of 9-(N-phenylamino)-9-fluorenecarboxylic acid, respectively. Some initial success in extending the scope of this reaction to other substrates, such as benzophenone, has been achieved by using other epimetallating agents, like the presumed LiV(CH3)2 and Ti(OPri)2. A brief review of the processes and organic synthetic applications of epimetallation and transfer epimetallation of C–C π-bonds is offered as background.

Graphical abstractThe feasibility of hydrocarboxylating carbonyl and imino derivatives by a two-step process of epimetallation and carbonation has been demonstrated with 9-fluorenone and 9-fluorenone anil. With LiVH2 as the epimetallating agent, the process yielded 75% of 9-hydroxy-9-fluorenecarboxylic acid and 65% of 9-(N-phenylamino)-9-fluorenecarboxylic acid. Epimetallating reagents of vanadium and titanium also show promise.Figure optionsDownload full-size imageDownload as PowerPoint slide