Visible-Light-Mediated Annulation of Electron-Rich Alkenes and Nitrogen-Centered Radicals from <i>N</i>-Sulfonylallylamines: Construction of Chloromethylated Pyrrolidine Derivatives

Crespin, Lorène; Greb, Andreas; Blakemore, David C.; Ley, Steven V.

doi:10.1021/acs.joc.7b02146

Cited by 23 publications

(21 citation statements)

References 66 publications

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“…Important contributions by Suárez, Muñiz, Nagib, and others show that amidyl radicals generated from N-iodinated or -brominated amides can initiate the remote C(sp 3 )–H activation through a intramolecular 1,5-hydrogen-atom-transfer process, followed by halogenation and cyclization, thereby enabling the construction of various nitrogen heterocycles. Apart from these N-radical precursors, N-chlorinated amides are also used to produce amidyl radicals that can engage in a series of radical transformations, such as remote C–H chlorination and chloramination of alkenes . Compared with the aforementioned haloamides, N-fluorinated amides exhibit much higher air, moisture, and thermal stability .…”

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confidence: 99%

Manganese-Catalyzed N–F Bond Activation for Hydroamination and Carboamination of Alkenes

et al. 2020

Org. Lett.

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A visible-light-promoted method for generating amidyl radicals from N-fluorosulfonamides via a manganesecatalyzed N−F bond activation strategy is reported. This protocol employs a simple manganese complex, Mn 2 (CO) 10 , as the precatalyst and a cheap silane, (MeO) 3 SiH, as both the hydrogen-atom donor and the F-atom acceptor, enabling intramolecular/intermolecular hydroaminations of alkenes, two-component carboamination of alkenes, and even three-component carboamination of alkenes. A wide range of valuable aliphatic sulfonamides can be readily prepared using these practical reactions.

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confidence: 99%

Manganese-Catalyzed N–F Bond Activation for Hydroamination and Carboamination of Alkenes

et al. 2020

Org. Lett.

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“…[42] Crespin et al disclosed a strategy for the challenging [3 + 2] cycloaddition of N-haloallylamines onto both electron-rich and electron-neutral alkenes (Scheme 25). [43] The N-chloro substrates 51 were prepared through the in-situ halogenation of the corresponding free amine 50 using 1,3-dichloro-5,5-dimethylhydantoin, which acted as both the chlorine and nitrogen source. The transition metal-based photocatalyst Ir(dF(CF 3 )ppy) 2 (bpy)PF 6 and the organic dye 9-mesityl-10-phenylacridinium tetrafluoroborate (PC-3) both acted as photosensitizers.…”

Section: Cà N/cà X Bond Formationsmentioning

confidence: 99%

Visible‐Light‐Catalyzed N‐Radical‐Enabled Cyclization of Alkenes for the Synthesis of Five‐Membered N‐Heterocycles

Wang

Guo

et al. 2021

ChemSusChem

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Five-membered N-heterocycles play an important role in organic synthesis and material chemistry, as they are widespread through pharmaceutical molecules and natural products. Chemists have developed many synthetic strategies for constructing five-membered N-heterocycles from N-centered radicals, but the availability of mild and green methods for these transformations is still limited. The cyclization of visible-lightgenerated N-centered radicals with alkenes has emerged as a powerful tool to enable these chemical transformations in recent years. Through chosen representative examples, the significant developments in this promising field were outlined, including the selection of catalysts, substrate scope, mechanistic understanding (especially density functional theory calculations), and applications. The contents of this Minireview are categorized by intramolecular cyclization and intermolecular Ncentered radical addition/cyclization reactions.

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“…Found in natural products, biomolecules, and catalysts, pyrrolidines are ranked among the most popular nonplanar heterocycles and numerous methodologies have consequently been developed to prepare them . The main strategies leading to such structures rely on metal-catalyzed − or organocatalyzed − [3 + 2] cycloadditions, Tsuji–Trost cyclizations, cyclopropane ring openings with imine, and organo-singly-occupied molecular orbital (SOMO) cycloaddition of β-amino aldehydes and olefins . Another general approach entails the hydroamination cyclization of alkynes (Scheme A) .…”

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confidence: 99%

H-bonding vs Protonation of Alkynes in Regioselective Hydroamination Reactions: A Glimpse into the Reactivity of Arylogous Ynolethers and Ynamines

et al. 2019

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In this paper is described the competition and transition between hydrogen bonding and protonation of alkynes connected, on one side, to various aromatic rings and to chiral amino ester appendages on the other side. While the first mode of activation induced the cyclization into pyrrolidines, the protonation of the alkyne led preferentially to tetrahydropyridines due to the higher level of the highest occupied molecular orbital (HOMO) of the considered arylogous ynolethers and ynamines. The transition between H-bonding and protonation was observed with the alkyne substituted with 2-methoxyphenyl, for which the cyclization delivered either five- or six-membered rings depending on the temperature of the experiment. From there, the cyclization of dialkoxy- and trialkoxyphenyl-substituted alkynes into six-membered rings, i.e., tetrahydropyridines, was developed. When next applied to alkynylindoles, the same pattern of cyclization provided six-membered rings as an illustration of the reactivity of arylogous ynamines. Thanks to the high reactivity of the intermediate cationic species, weak nucleophiles such as NH-oxazolidinone participated efficiently in the hydroamination reaction of alkynylindoles. Pyrrolidines, tetrahydropyridines, and piperidines decorated with various aromatics and substituents were thus prepared in enantio- and stereoselective manner. Capitalizing on the enamine moiety of the azaheterocycles, the molecular diversity was extended through stereoselective oxidation and ring contraction processes.

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Visible-Light-Mediated Annulation of Electron-Rich Alkenes and Nitrogen-Centered Radicals from N-Sulfonylallylamines: Construction of Chloromethylated Pyrrolidine Derivatives

Cited by 23 publications

References 66 publications

Manganese-Catalyzed N–F Bond Activation for Hydroamination and Carboamination of Alkenes

Manganese-Catalyzed N–F Bond Activation for Hydroamination and Carboamination of Alkenes

Visible‐Light‐Catalyzed N‐Radical‐Enabled Cyclization of Alkenes for the Synthesis of Five‐Membered N‐Heterocycles

H-bonding vs Protonation of Alkynes in Regioselective Hydroamination Reactions: A Glimpse into the Reactivity of Arylogous Ynolethers and Ynamines

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