Recent Advances in the Catalytic Dearomatization of Naphthols

Abstract

The catalytic dearomatization of naphthols offers a unique platform to rapidly access structurally complex and densely functionalized molecular architectures. Thermodynamically more favorable, with respect to the analogous phenol‐variant, the transformation of the phenolic ring into the corresponding naphthalenone (cited here as naphthyl dearomatization) has faced a considerable amount of attention over the past decade with constant improvements towards stereocontrol. A collection of the most representative and recent catalytic variants involving carbon–carbon as well as carbon–heteroatom bond forming events are presented in this Minireview article.

Recent Advances in the Construction of Spiro Compounds via Radical Dearomatization

“…Reviews on oxidative ipso-annulation towards spirocycles mainly focus on transition metal-catalyzed, nucleophilic or electrophilic dearomatization processes, whereas radical-initiated dearomatizing spirocyclization of aromatics is underrepresented. [2,3,6] In this review, we summarize recent ten-year advances in the field of radical-initiated dearomative reactions for the construction of spirocycles. In addition, the reaction design, mechanism and applicability of spirocyclic compounds via ipso-cyclization towards the synthesis of complex molecules will also be covered.…”

Synthesis of Perinaphthenones via BF3.Et2O Mediated One‐Pot Cascade 4,5‐Annulation Reactions of 1‐Naphthols and Ynones

“…[1] In general, annulations of naphthols involved either transition metal catalyzed C-H activation with alkynes [2] or intramolecular annulations pre-functionalized naphthols by various oxidants. [3] Moreover, a wide range of reports on annulations of β-naphthol are reported. [4] However, annulations of α-naphthol are remaining underdeveloped.…”

Radical‐Mediated Non‐Dearomative Strategies in Construction of Spiro Compounds

“…Despite of many known procedures of rigid spirocyclic scaffold preparation, access to diversely functionalized molecules mostly rely on dearomatization of starting material. [7] Dearomatization reactions are the most powerful and versatile organic transformations, that allows for both effective construction of cyclic derivatives and functionalization of forming system from readily available and simple starting materials. [8] This powerful strategy allows for construction of complex scaffolds with three-dimensional and well-defined structures from planar, easily available aromatic derivatives.…”

“…As a consequence, a number of radical-mediated methods that allows for the transformation of aromatic system into functionalized spirocyclic molecules have been developed. [7] Notable advance of dearomative radical spirocyclizations is the simplicity and easy access to the starting material. However, most of the libraries prepared using this concept comprise structure similarity.…”