Catalytic Asymmetric Dearomatization by Transition-Metal Catalysis: A Method for Transformations of Aromatic Compounds

Abstract

Catalytic asymmetric dearomatization (CADA) reactions refer to those reactions converting aromatic compounds into enantio-enriched three-dimensional cyclic molecules in a catalytic fashion. In the past, this area has seen significant progress since a series of valuable strategies for asymmetric catalysis were successfully applied. In this review, we provide insightful discussions on recent representative examples of asymmetric dearomatization reactions catalyzed by transition-metal complexes. Close attention is paid to the mechanism, scope, limitations, and the future direction of CADA reactions.

Synthetic Approaches to Tetracyclic Indolines as Versatile Building Blocks of Diverse Indole Alkaloids

“…[50] As depicted in Scheme 19, ap alladium-catalyzed Buchwald-Hartwiga mination of o-dibromobenzene with aniline 157,o btained from commerciallya vailables tartingm aterial 156 through N-protection generated the compound 158.T hen, the introduction of the N-phosphoramide group and deprotection of the methoxy group are essential for the achievemento fe xcellent chemoselectivity in the palladium-catalyzed intramolecular dearomative cyclization. [51] The fourth ring was introduced by aTMSOTf-promotedd eprotection of Boc group and an in situ intramolecular aza-Michael addition cascade reaction.…”

Oxidative Coupling of 3‐Oxindoles with Indoles and Arenes

“…[1] Many efforts to synthesize these types of molecular frameworks have relied upon rearrangements and cyclization reactions that require designed substrates or strongly acidic/basic conditions, limiting functional group compatibility. [2] Recent adventsi no xidative dearomatization [3] chemistry have allowed am ore convergent approacht ot he synthesis of 2,2,-disubstitutedi ndolin-3-one scaffolds.…”

Palladium‐Catalyzed Dearomativesyn‐1,4‐Carboamination with Grignard Reagents

“…[4] Thus,t hese processes have also provided significant advantages in expediting syntheses of natural products and bioactive compounds. Fori nstance,t he catalytic dearomatization of arenes has gained much attention in recent years, [6] whereas the application of such transformations has largely been limited to specific classes of activated arenes such as naphthols, [7] naphthylamines, [8] heteroarenes, [9] and arenes bearing benzylic heteroatoms. Fori nstance,t he catalytic dearomatization of arenes has gained much attention in recent years, [6] whereas the application of such transformations has largely been limited to specific classes of activated arenes such as naphthols, [7] naphthylamines, [8] heteroarenes, [9] and arenes bearing benzylic heteroatoms.…”

“…[5] Nevertheless,d espite these notable advancements in the field, there still remains several challenges to be addressed. Fori nstance,t he catalytic dearomatization of arenes has gained much attention in recent years, [6] whereas the application of such transformations has largely been limited to specific classes of activated arenes such as naphthols, [7] naphthylamines, [8] heteroarenes, [9] and arenes bearing benzylic heteroatoms. [10] Dearomative conversions of simple,n onactivated arenes in ac atalytic manner are rare,e specially the variants which concurrently introduce functionality other than hydrogen.…”