This Review summarizes the development of catalytic asymmetric dearomatization (CADA) reactions. The CADA reactions discussed herein include oxidative dearomatization reactions, dearomatization by DielsAlder and related reactions, the alkylative dearomatization of electron-rich arenes, transition-metal-catalyzed dearomatization reactions, cascade sequences involving asymmetric dearomatization as the key step, and nucleophilic dearomatization reactions of pyridinium derivatives. Asymmetric dearomatization reactions with chiral auxiliaries and catalytic asymmetric reactions of dearomatized substrates are also briefly introduced. This Review intends to provide a concept for catalytic asymmetric dearomatization.

Catalytic Asymmetric Dearomatization Reactions

Evolution in the field of the total synthesis of natural products has led to exciting developments over the last decade. Numerous chemoselective and enantioselective methodologies have emerged from total syntheses, resulting in efficient access to many important natural product targets. This Review highlights recent developments concerning dearomatization, a powerful strategy for the total synthesis of architecturally complex natural products wherein planar, aromatic scaffolds are converted to three-dimensional molecular architectures.

Dearomatization Strategies in the Synthesis of Complex Natural Products

Advances in dearomatization strategies of indoles

Dearomatization reactions provide the most efficient method for the synthesis of spiro- or fused-ring systems from readily available compounds. This review summarizes the recent developments in dearomatization reactions of indoles, pyridines, quinolines, isoquinolines, and some other heteroaromatic compounds. The applications of these methods in total synthesis of natural products are also briefly introduced.

Recent advances in dearomatization of heteroaromatic compounds.

Nucleophilic dearomatizing (DNAr) reactions of aromatic C,H-systems. A mature paradigm in organic synthesis.

Regioselective functionalisation of nitrobenzene and benzonitrile derivatives via nucleophilic aromatic substitution of hydrogen by phosphorus-stabilized carbanions

Carmen M. Andujar Sanchez

Papers

Nucleophilic dearomatizing (DNAr) reactions of aromatic C,H-systems. A mature paradigm in organic synthesis.

Regioselective functionalisation of nitrobenzene and benzonitrile derivatives via nucleophilic aromatic substitution of hydrogen by phosphorus-stabilized carbanions

Nucleophilic aromatic substitution of hydrogen through lithiated phosphine borane complexes and N-phosphorylphosphazenes

Synthesis of functionalised cyclohexadienes through addition of lithiated phosphine borane complexes to benzonitriles

Dearomatisation of 1- and 2-cyanonaphthalene through nucleophilic conjugate addition