Achievements, Challenges, and Scope of Thirty Years of Work on the Biotransformation of Arenes and Their Synthetic Applications

Abstract

This paper is dedicated to the memory of Tomas Hudlicky who mentored us with dedication and generosity in the art of chemoenzymatic synthesis, contributing to the development of this area in Uruguay.

Visible Light-Mediated Dearomative Spirocyclization/Imination of Nonactivated Arenes through Energy Transfer Catalysis

“…10,11 Transition-metal-mediated dearomatizations have been widely used and enable elaborate functionalization schemes (Figure 1, top left) through coordination, electrophilic attack, nucleophilic attack, and decomplexation mechanism. 12 Dearomative oxidation manifolds encompasses phenol oxidation 13 and radical-mediated oxidation [14][15][16][17][18] (Figure 1, top left) that provide cyclohexadienones derivatives from the corresponding phenols or aryl ethers or microbial oxidations of monosubstituted arenes; 19 however, both of these reactions are hampered by limitations in the substrate scope. Dearomative photocycloadditions have the ability to increase the structural complexity through the formation of bridged or fused bicyclic dearomatized products via [2 + 2], [3 + 2], and [4 + 2] cycloadditions, 6,11,[20][21][22][23][24][25][26][27] (Figure 1, top right) and in some cases the fused bicycles can undergo cycloreversion/fragmentation to yield dearomatized difunctionalized cyclic products (Figure 1, top right).…”