Recent advances in the dearomative functionalisation of heteroarenes

Abstract

This Perspective outlines the myriad of products that can be obtained by the dearomatisation and functionalization of heteroarene substrates. Complex 3D molecules can often be prepared in one step from simple arene starting materials.

Catalyst-Controlled Enantioselective and Regiodivergent Addition of Aryl Boron Nucleophiles to N-Alkyl Nicotinate Salts

“…In this context, pyridinium salts are multident electrophiles that, in the presence of nucleophiles, can undergo (1,2), (1,4), or (1,6) addition to afford the corresponding dihydropyridines (DHPs). − These scaffolds are useful intermediates for the preparation of nonaromatic nitrogen heterocycles (Figure A) . Directing a nucleophile to a specific site on the ring has proven to be a nontrivial task.…”

Dearomative intermolecular [2 + 2] photocycloaddition for construction of C(sp3)-rich heterospirocycles on-DNA

“…45 New heteroarene dearomative functionalization strategies have recently demonstrated great value, particularly those enabled by visible light, enhancing the molecular complexity and threedimensionality of these venerable products. 46 Additionally, BMS in collaboration with the Knowles laboratory reported a Please do not adjust margins Please do not adjust margins different [2+2] photocycloaddition to access polysubstituted (hetero)spiro [3.3]heptane products. 12 A recent collaborative study from our groups focused on unlocking the radical reactivity of 1,3-disubstituted [1.1.1]bicyclopentyl (BCP) halides for on-DNA reactions.…”

“…45 New heteroarene dearomative functionalization strategies have recently demonstrated great value, particularly those enabled by visible light, enhancing the molecular complexity and threedimensionality of these venerable products. 46 Additionally, BMS in collaboration with the Knowles laboratory reported a different [2 + 2] photocycloaddition to access polysubstituted (hetero)spiro [3.3]heptane products. 12 A recent collaborative study from our groups focused on unlocking the radical reactivity of 1,3-disubstituted [1.1.1]bicyclopentyl (BCP) halides for on-DNA reactions.…”

One-pot synthesis of 4-(imidazol-1-yl)indole derivatives through a sequential dearomatization and Ag-catalyzed cyclization/Cs2CO3-mediated addition/aromatization reaction

“…One of the powerful routes to complex heterocycles is the synthesis based on dearomatization of aromatic molecules. 10,11 Through oxidative dearomatization, o-alkynylanilines 1b,12 could be converted to the corresponding o-alkynyl cyclohexadienimines, which are useful starting Fig. 1 Some useful 4-(azol-1-yl)indole derivatives.…”