Visible‐Light‐Initiated Manganese Catalysis for C−H Alkylation of Heteroarenes: Applications and Mechanistic Studies

Nuhant, Philippe; Oderinde, Martins S.; Genovino, Julien; Juneau, Antoine; Gagné, Yohann; Allais, Christophe; Chinigo, Gary M.; Choi, Chulho; Sach, Neal W.; Bernier, Louise; Fobian, Yvette M.; Bundesmann, Mark W.; Khunte, Bhagyashree; Frenette, Mathieu; Fadeyi, Olugbeminiyi O.

doi:10.1002/anie.201707958

Cited by 162 publications

(65 citation statements)

References 43 publications

(18 reference statements)

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“…In 2017, Frenette,F adeyi and co-workers reported the use of visible-light-initiated manganese catalysis to enable Minisci-type alkylation from alkyl iodides. [134] Thehypothesis was that the weak Mn À Mn bond of Mn 2 (CO) 10…”

Section: Radicals From Alkyl Halidesmentioning

confidence: 99%

Recent Advances in Minisci‐Type Reactions

2019

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Reactions that involve the addition of carbon‐centered radicals to basic heteroarenes, followed by formal hydrogen atom loss, have become widely known as Minisci‐type reactions. First developed into a useful synthetic tool in the late 1960s by Minisci, this reaction type has been in constant use over the last half century by chemists seeking to functionalize heterocycles in a rapid and direct manner, avoiding the need for de novo heterocycle synthesis. Whilst the originally developed protocols for radical generation remain in active use today, they have been joined in recent years by a new array of radical generation strategies that allow use of a wider variety of radical precursors that often operate under milder and more benign conditions. The recent surge of interest in new transformations based on free radical reactivity has meant that numerous choices are now available to a synthetic chemist looking to utilize a Minisci‐type reaction. Radical‐generation methods based on photoredox catalysis and electrochemistry have joined approaches which utilize thermal cleavage or the in situ generation of reactive radical precursors. This review will cover the remarkably large body of literature that has appeared on this topic over the last decade in an attempt to provide guidance to the synthetic chemist, as well as a perspective on both the challenges that have been overcome and those that still remain. As well as the logical classification of advances based on the nature of the radical precursor, with which most advances have been concerned, recent advances in control of various selectivity aspects associated with Minisci‐type reactions will also be discussed.

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Section: Radicals From Alkyl Halidesmentioning

confidence: 99%

Recent Advances in Minisci‐Type Reactions

2019

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“…Mn(CO) 5 , thereby sustaining the radical chain. For path a and path b , we currently consider that path a might be a major reaction pathway due to the low BDE of R f −I bond (Mn−I bond BDE=67 kcal mol −1 vs C 4 F 9 −I bond BDE=49 kcal mol −1 ) and the low concentration of IMn(CO) 5 compared to R f I. However, the possibility of path b can be not completely excluded, and this process is likely to represent a minor reaction pathway.…”

Section: Resultsmentioning

confidence: 99%

Intermolecular Iodofluoroalkylation of Unactivated Alkynes and Alkenes Mediated by Manganese Catalysts

Wang

Guo

et al. 2020

Adv Synth Catal

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An approach for iodofluoroalkylation of unactivated alkynes and alkenes facilitated by an earth‐abundant and inexpensive manganese catalyst, Mn2(CO)10, is reported. This protocol employs visible light as the energy input and shows a wide substrate scope and high functional‐group compatibility. A variety of synthetically useful fluoroalkylated alkyl and alkenyl iodides can be prepared in moderate to excellent yields. The reaction features high efficiency, operational simplicity, scalability, as well as excellent chemo‐, regio‐, and E/Z selectivities.

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“…Darüber hinaus berichteten Frenette und Fadeyi über ein Mangansystem für die direkte Alkylierung von Lepidin, sowie einiger anderer Azine, mit primären, sekundären und tertiären Alkyliodiden unter Bestrahlung mit blauem LED‐Licht [Schema , Gl. (2)] . Dieses Verfahren konnte auch zur effizienten Alkylierung einiger Wirkstoffe in einem späten Synthesestadium angewendet werden.…”

Section: Alkylierung Von Heteroarenenunclassified

Jenseits von Friedel und Crafts: immanente Alkylierung von C‐H‐Bindungen in Arenen

Evano

Theunissen

2019

Angewandte Chemie

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Alkylierte Arene sind allgegenwärtige Moleküle und Bausteine in vielen Bereichen der Naturwissenschaften. Die nur scheinbar einfache regioselektive Alkylierung von Arenen ist tatsächlich in vielen Fällen noch immer eine anspruchsvolle Transformation. Klassische Methoden zur Einführung von Alkylgruppen in Arene, wie die Friedel‐Crafts‐Reaktion, Radikaladditionen, die Metallierung oder Präfunktionalisierung von Arenen mit anschließender Alkylierung, ebenso wie Alternativen wie die dirigierte Alkylierung von C‐H‐Bindungen, zeigen noch immer gravierende Einschränkungen hinsichtlich der Anwendungsbreite, Effizienz und Selektivität. Diese können durch die Ausnutzung der immanenten Reaktivität einiger (Hetero)Arene umgangen werden, in denen elektronische und sterische Eigenschaften, die durch ein (oder mehrere) vorhandene(s) Heteroatom(e) bestimmt werden (oder nicht bestimmt werden), eine hohe Regioselektivität gewährleisten. Dieser Aufsatz bietet einen umfassenden Überblick über die immanenten Alkylierungen von (Hetero)Arenen.

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Visible‐Light‐Initiated Manganese Catalysis for C−H Alkylation of Heteroarenes: Applications and Mechanistic Studies

Cited by 162 publications

References 43 publications

Recent Advances in Minisci‐Type Reactions

Recent Advances in Minisci‐Type Reactions

Intermolecular Iodofluoroalkylation of Unactivated Alkynes and Alkenes Mediated by Manganese Catalysts

Jenseits von Friedel und Crafts: immanente Alkylierung von C‐H‐Bindungen in Arenen

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