Synthesis of Altenuene Backbones through Iodine(III)-Participated Umpolung Diesterification and Insights into the General [1,5]-H Shift in para-Dearomatization of Phenols via Quantum Chemical Calculations

Abstract

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

Metal -free PhI(OAc)2-oxidized decarboxylation of propiolic acids towards synthesis of α-acetoxy ketones and insights into general decarboxylation with DFT calculations

“…Based on our previous work on the synthesis of α-cyano ketones through cyanidation of silyl enol ethers promoted by hypervalent iodine 17 and oxidative C–O formation from electron-rich carbons via the umpolung process, 18 in the current work we set out to make progress on PhI(OAc) 2 -oxidative decarboxylation of propiolic acids for the synthesis of α-acetoxy ketones.…”

Synthesis of fluorinated polycyclic dehydroaltenusin analogs through hypervalent iodine-catalyzed dearomatization

“…6 Very recently, we uncovered a method for introducing electron-withdrawing groups, such as acetoxy groups, into the dehydroaltenusin backbone structure (Scheme 1). 7 Based on this background, the introduction of a fluorine atom into the dehydroaltenusin backbone structure to get corresponding polycyclic analogs attracted our interest. And, in the continuation of our previous work, 8 we herein hypothesized that similar lactonization and dearomatization should proceed through the in situ PhIF 2 synthesis strategy, affording fluorinated dehydroaltenusin analogs.…”