Synthesis of Ortho-Functionalized 1,4-Cubanedicarboxylate Derivatives through Photochemical Chlorocarbonylation

The cubane ring has received intense attention as a 3D benzene isostere and scaffold. Mono- and 1,4-disubstituted cubanes are well-described. Here we report a practical procedure for a direct radical-mediated chlorocarbonylation process initially reported by Bashir-Hashemi, to access a range of 2-substituted 1,4-cubanedicarboxylic ester derivatives. A subsequent regioselective ester hydrolysis to give fully differentiated 1,2,4-trisubstituted cubanes is demonstrated.

Automated summary

The article presents a practical procedure for preparing a range of 2-substituted 1,4-cubanedicarboxylic ester derivatives through a radical-mediated chlorocarbonylation process, along with a subsequent regioselective ester hydrolysis to obtain fully differentiated 1,2,4-trisubstituted cubanes.