Copper‐Catalyzed Rearrangement of <i>N</i>‐Aryl Nitrones into Epoxyketimines

Mo, Dong‐Liang; Anderson, Laura L.

doi:10.1002/ange.201301963

Cited by 9 publications

(1 citation statement)

References 36 publications

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“…Cascade reactions are important and proficient transformations that rapidly build molecular complexity and have been employed for the synthesis of complex molecules in both target‐ and diversity‐oriented syntheses 2–4. While pursuing our interest in the reactivity of α,β‐unsaturated N ‐aryl nitrones as precursors to highly functionalized molecules, we decided to test their reactivity toward electron‐deficient allenes (Scheme ) 5. To our delight, we discovered that either dihydrocarbazoles 1 or dihydropyridoindoles 2 can be formed as the sole products of the reaction of N ‐aryl‐α,β‐unsaturated nitrones 3 with electron‐deficient allenes 4 depending on the choice of solvent (Scheme ) 6.…”

Section: Introductionmentioning

confidence: 99%

Solvent‐Controlled Bifurcated Cascade Process for the Selective Preparation of Dihydrocarbazoles or Dihydropyridoindoles

Wink

Anderson

2014

Chemistry A European J

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A solvent-controlled cascade process has been identified for the dual purpose of the preparation of either dihydrocarbazoles or dihydropyridoindoles from identical N-aryl-α,β-unsaturated nitrones and electron-deficient allene starting materials. These reactions proceed smoothly under mild metal-free conditions affording a range of two types of skeletally distinct indole-based heterocycles in high yield and diastereoselectivity. These transformations demonstrate the use of a bifurcated cascade process that hinges on the ring-opening event of a benzazepine intermediate for the synthesis of skeletally diverse heterocyclic products and rapid access to biologically-significant, indole-based structures.

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Section: Introductionmentioning

confidence: 99%

Solvent‐Controlled Bifurcated Cascade Process for the Selective Preparation of Dihydrocarbazoles or Dihydropyridoindoles

Wink

Anderson

2014

Chemistry A European J

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Synthesis of N‐Aryl Isoxazolidines by Photo‐Promoted N‐Selective Arylation of Oximes and Cyclization Using Hypervalent Iodine Reagents and Copper Catalyst

et al. 2023

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Oximes cause photo‐promoted, copper‐catalyzed N‐selective arylation with diaryl iodonium salts to produce nitrones, which in turn undergo intra‐ or intermolecular 1,3‐dipolar cyclization with olefins to afford N‐aryl isoxazolidines. Hypervalent iodine reagents substituted with either electron‐rich or electron‐deficient groups afford the corresponding N‐aryl isoxazolidines in 26–95% yields. This method offers a faster reaction rate, lower catalyst loading and broader substrate scope of oxime than similar nitrone syntheses employing Chan‐Lam‐Evans coupling. The reaction involves via a radical/single electron transfer (SET) pathway, and does not proceed in the absence of photoirradiation.

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Diverse Applications of Nitrones for the Synthesis of Heterocyclic Compounds

Anderson

2015

Asian J Org Chem

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Although best known for their [3+ +2]-dipolar cycloaddition reactivity and use in the preparationo fi soxazolines and isoxazolidines,n itrones are versatile reagents that undergo av ariety of transformationsf or the synthesis of ad iverse array of heterocyclic compounds. Theb readth of heterocycle synthesis using nitrone reagentsi ncludes: 1) stepwise [3+ +3]-cycloaddition reactions of nitrones with vinyl diazoacetates, transition-metal-coordinated cycloisomerization intermediates, trimethylenem ethanes, and cyclopropane diesters to form dihydro-a nd tetrahydro-1,2-oxazines;2 )internal redox cyclization reactions of alkyne-tetheredn itrones to provide access to azabicyclooctanes,i soindoles, aminoindanones, and isoquinolones;3 )electrocyclizationso fi ns itu generated N-allenylnitrones to form pyridines and azetidine-N-oxides, as well as metal-catalyzed cyclizationsa nd rearrangements of nitrones to form azepine-N-oxides, spirocyclic isoxazolines, and a,b-epoxyimines;a nd 4) the use of [3+ +2]cycloaddition reactions of nitrones to trigger cascade reactions for the formationo ft etrahydrooxazepines, dihydrocarbazoles, and benzoindolizines. This Focus Review aims to highlight these diverse applicationso fn itrones for the synthesis of heterocyclest oe mphasize the broad utility of these reactive intermediates andt oi nspire their furtherd evelopment as important synthons beyond the scope of traditional [3+ +2]-dipolar cycloaddition reactions. Scheme1.[3+ +2]-Dipolar cycloadditions of nitrones and their application to the synthesis of naturalproducts and biologically active compounds:Diverse applicationsofn itrones for the synthesis of heterocyclic compounds.[a] Prof. Dr.L.L.A nderson 2. Formal [3+ +3]-Cycloadditions of Nitrones and [4+ +2]-Cycloadditions of N-Alkenylnitrones.Formal [3+ +3]-cycloadditions of nitrones have been investigated as alternative methods for the synthesis of dihydro-and tetrahydro-1,2-oxazines and offer new routes to these heterocycles that are unique from traditional [4+ +2]-cycloadditions of dienes and nitrosobenzenes. [8] The nitrone cycloaddition partners discussed below include vinyldiazoacetates, alkenyl gold complexes,m etal carbenoids generated through cycloisomerization processes, trimethylene methanes, and cyclopropane diesters (Scheme 3A). The synthesiso fN-alkenylnitrones has also prompted an investigation of these electron-deficient azadienesa si nverse-demand cycloaddition partners for the synthesis of six-membered-ring nitrones that are poised to undergo furtherf unctionalization (Scheme 3B). Prof. Laura L. Anderson receivedh er B.A. from Knox College in 2000 and moved to the University of California, Berkeley,f or her graduate studies where she worked with Prof. John Arnold and Prof. Robert G. Bergman developing new hydroamination catalystsa nd studying the reactivity of transition metal imido complexes. After obtaining her Ph.D. in 2005, Prof. Anderson movedt ot he Universityo f California, Irvine, wheres he completed aR uth L. Kirschstein NIH postdoctoral fellowship with Pr...

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Copper‐Catalyzed Rearrangement of N‐Aryl Nitrones into Epoxyketimines

Cited by 9 publications

References 36 publications

Solvent‐Controlled Bifurcated Cascade Process for the Selective Preparation of Dihydrocarbazoles or Dihydropyridoindoles

Solvent‐Controlled Bifurcated Cascade Process for the Selective Preparation of Dihydrocarbazoles or Dihydropyridoindoles

Synthesis of N‐Aryl Isoxazolidines by Photo‐Promoted N‐Selective Arylation of Oximes and Cyclization Using Hypervalent Iodine Reagents and Copper Catalyst

Diverse Applications of Nitrones for the Synthesis of Heterocyclic Compounds

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