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

Advances in dearomatization strategies of indoles

Dieser Aufsatz fasst die bisherigen Entwicklungen auf dem Gebiet der katalytischen asymmetrischen Desaromatisierungen (CADAs) zusammen. Die hier diskutierten katalytischen asymmetrischen Desaromatisierungen umfassen oxidative Desaromatisierungen, Desaromatisierungen durch Diels-Alder- und verwandte Reaktionen, alkylierende Desaromatisierungen elektronenreicher Arene, Ubergangsmetall-katalysierte Desaromatisierungen, Kaskadensequenzen mit asymmetrischer Desaromatisierung sowie nucleophile Desaromatisierungen von Pyridinium-Derivaten. Zudem werden kurz asymmetrische Desaromatisierungen mithilfe chiraler Auxiliare sowie katalytische asymmetrische Reaktionen mit desaromatisierten Substraten eingefuhrt. Ziel dieses Aufsatzes ist es, ein Konzept fur die asymmetrische Desaromatisierung zu liefern.

Katalytische asymmetrische Desaromatisierungen

In some cases, the imine functionality of the indolenines, which are obtained from the allylic dearomatization, causes purification difficulties.

Enantioselective synthesis of spiro cyclopentane-1,3'-indoles and 2,3,4,9-tetrahydro-1H-carbazoles by iridium-catalyzed allylic dearomatization and stereospecific migration.

Catalytic asymmetric dearomatization (CADA) reaction-enabled total synthesis of indole-based natural products

A total synthesis of the marine natural product diazonamide A (1) has been accomplished. This work features a highly stereoselective synthesis of the C(10) quaternary center and the central furanoindoline core enabled by an iminium-catalyzed alkylation–cyclization cascade. Additionally, a magnesium-mediated intramolecular macroaldolization and a palladium-catalyzed tandem borylation/annulation were developed to enable the closure of the two 12-membered macrocycles of diazonamide A. This synthesis involves 20 steps in its longest linear sequence and proceeds in 1.8% overall yield.

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Christopher J. Sinz

Papers

Total synthesis of diazonamide A