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. 2021;53(10):1734-1748.
doi: 10.1055/s-0040-1705995.

Recent Advances in the Development of Catalytic Methods that Construct Medium-ring Lactams, Partially Saturated Benzazepines and their Derivatives

Wrickban Mazumdar  1 , Tom G Driver  1
Affiliations

Recent Advances in the Development of Catalytic Methods that Construct Medium-ring Lactams, Partially Saturated Benzazepines and their Derivatives

Wrickban Mazumdar et al. Synthesis (Stuttg). 2021.

Abstract

Recent catalytic methods to construct medium-sized lactams and partially saturated benzazepines and their derivatives are surveyed. The review is divided into the following sections: 1 Introduction 2 Non-Transition Metal Catalyzed Reactions 2.1 Beckmann Rearrangement 2.2 Non-Beckmann Rearrangement Reactions 2.3 Multi-component reactions 3 Transition Metal-Catalyzed Reactions 3.1 Au-catalyzed reactions to access medium-sized N-heterocycles 3.2 Reactions involving a metal η3-complex catalytic intermediate 3.3 Transition metal-catalyzed reactions of strained cycloalkanes 4 Conclusions.

Keywords: Beckmann rearrangement; benzazepine; benzazepinone; caprolactam; medium-ring N-heterocycle.

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Figures

Scheme 1.
Scheme 1.
Bioactive compounds that contain partially saturated benzazepine cores.
Scheme 2.
Scheme 2.
Development of cyanuric chloride-catalyzed Beckmann rearrangement.
Scheme 3.
Scheme 3.
Development of TAPC-catalyzed Beckmann rearrangement.
Scheme 4.
Scheme 4.
Development of a cyclopropenium-mediated Beckmann rearrangement.
Scheme 5.
Scheme 5.
Development of Ca-catalyzed Beckmann rearrangement.
Scheme 6.
Scheme 6.
Boronic Acid Catalysis (BAC) strategy to assemble medium-ring lactams.
Scheme 7.
Scheme 7.
Transoximation to access medium-ring lactams.
Scheme 8.
Scheme 8.
Cooperative organocatalytic Rauhut–Currier reaction to construct azepino[1,2-a]indoles.
Scheme 9.
Scheme 9.
Brønsted acid-catalyzed π-(7-endo-trig) cyclization to access medium-ring lactams.
Scheme 10.
Scheme 10.
Development of an aza-Piancatelli cyclization-Michael addition tandem reaction to access bicyclic medium-ring N-heterocycles.
Scheme 11.
Scheme 11.
Development of a chiral amine-catalyzed [4+3] cyclization reaction to access spirocyclic azepines.
Scheme 12.
Scheme 12.
Development of four component azide-Ugi reactions to access benzodiazepines.
Scheme 13.
Scheme 13.
Development of four component Ugi reactions.
Scheme 14.
Scheme 14.
Chiral amine-catalyzed reactions to access medium-ring lactams through LUMO lowering.
Scheme 15.
Scheme 15.
Iron-catalyzed Prins-cyclization/halogenation sequence to access medium ring N-heterocycles.
Scheme 16.
Scheme 16.
Cu-Catalyzed three component coupling / Pd-catalyzed hydroarylation two-step protocol to construct medium-ring N-heterocycles.
Scheme 17.
Scheme 17.
Au-Catalyzed oxidative cyclization of tertiary anilines to synthesize tetrahydrobenz[b]azepin-4-ones.
Scheme 18.
Scheme 18.
Au-Catalyzed oxidative [5+2] cyclization reaction.
Scheme 19.
Scheme 19.
Au-Catalyzed intramolecular redox reaction of yne-enones to access tetrahydroazepines.
Scheme 20.
Scheme 20.
Cooperative catalysis for the regio- and enantioselective annulation of enals and benzoxazinanones to create benzazepinones.
Scheme 21.
Scheme 21.
Cooperative NHC- and Pd catalytic cycles for benzazepinones.
Scheme 22.
Scheme 22.
Cooperative DABCO-Ir(I) catalysis to synthesize
Scheme 23.
Scheme 23.
Pd-Catalyzed asymmetric [4+3] cycloaddition to synthesize benzofuro[3,2-b]azepines.
Scheme 24.
Scheme 24.
Rh-Catalyzed “capture-collapse” approach to transform aminocyclopropanes into benzazepinones.
Scheme 25.
Scheme 25.
Rh2(II)-Catalyzed reaction of ortho-cyclobutanol substituted aryl azides to construct benzazepinones.
Scheme 26.
Scheme 26.
Catalytic cycle involving a putative Rh2(II)- N-aryl nitrene.
Scheme 27.
Scheme 27.
I(III)-Mediated oxidative cyclization-migration to access benzazepinones.
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