Synthesis of Altenuene Backbones through Iodine(III)-ParticipatedUmpolung Diesterification and Insights into the General [1,5]-HShift inpara-Dearomatization of Phenols via Quantum Chemical Calculations

Through PhI(OAc)2-oxidized dearomatization and diesterification of 3 '-hydroxy-[1,1 '-biphenyl]-2-carboxylic acids, aseries of polycyclic compounds possessing an altenuene backbone were obtained in moderate to good yields. The Umpolungdiesterification reaction was completed under mild reaction conditions without an additional nucleophilic reagent. This work offers aconcise method for the synthesis of diverse natural altenuene analogues. The mechanism was proposed, and the [1,5]-H shift wasstudied in isomerization from the ketone-form structure to a phenol employing computational studies.

Automated summary

In this study, a series of polycyclic compounds with altenuene backbone were successfully synthesized through PhI(OAc)2-oxidized dearomatization and diesterification. The Umpolung diesterification reaction occurred under mild conditions without the need for an additional nucleophilic reagent. This provides a concise method for the synthesis of diverse natural altenuene analogues.