Effect of Brønsted acids on the thiophenol-mediated radical addition–translocation–cyclization process for the preparation of pyrrolidine derivatives

Soulard, Valentin; Dénès, Fabrice; Renaud, Philippe

doi:10.1080/10715762.2016.1223294

Cited by 9 publications

(4 citation statements)

References 34 publications

(28 reference statements)

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“…[67] DØns, Renaud, and Soulard reported the effect of nitrogen protonation in propargylic amines on the thiophenol-mediated radical addition-translocation-cyclization (RATC) process for the synthesis of pyrrolidine derivatives. [68] N,N-Diisobutylpropargylamine was chosen as the model substrate for reaction screening. Theo ptimized con-ditions involved the use of AIBN (2 equiv), PhSH (2 equiv), and TFA( 10 equiv) in refluxing acetonitrile.U nder these conditions,t he cyclized pyrrolidine product was obtained in 78 %y ield.…”

Section: Reviewsmentioning

confidence: 99%

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Activation and Deactivation Strategies Promoted by Medium Effects for Selective Aliphatic C−H Bond Functionalization

Bietti

2018

Angew Chem Int Ed

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Selective functionalization of unactivated aliphatic C-H bonds represents an important goal of modern synthetic chemistry. Differentiating between such bonds in organic molecules with high levels of selectivity remains a crucial issue, and a profound understanding of even the subtlest reactivity trends is needed. Among the methods that have been developed, those based on hydrogen atom transfer (HAT) have attracted considerable interest. Within this framework, medium effects have proved effective in altering the reactivity and site selectivity in synthetically useful C-H functionalization procedures. In this Review, the mechanistic features behind the available strategies are discussed. It is shown that hydrogen bonding and acid-base interactions can promote C-H bond activation or deactivation toward HAT reagents, thereby providing fine-control over the site selectivity and product chemoselectivity as well as useful guidelines for future development and applications.

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Section: Reviewsmentioning

confidence: 99%

“…Dénès, Renaud, and Soulard reported the effect of nitrogen protonation in propargylic amines on the thiophenol‐mediated radical addition‐translocation‐cyclization (RATC) process for the synthesis of pyrrolidine derivatives . N , N ‐Diisobutylpropargylamine was chosen as the model substrate for reaction screening.…”

Section: C−h Bond Deactivationmentioning

confidence: 99%

Activation and Deactivation Strategies Promoted by Medium Effects for Selective Aliphatic C−H Bond Functionalization

Bietti

2018

Angew Chem Int Ed

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“…Dénès und Renaud berichteten über den Effekt der Stickstoffprotonierung in Propargylaminen auf den durch Thiophenol vermittelten Prozess aus radikalischer Addition, Translokalisation und Cyclisierung (RATC) für die Synthese von Pyrrolidinderivaten . Zum Screening der Reaktion wurde N , N ‐Diisobutylpropargylamin als Modellsubstrat ausgewählt.…”

Section: C‐h‐bindungsdeaktivierungunclassified

Anwendung von Mediumeffekten in Aktivierungs‐ und Deaktivierungsstrategien zur selektiven Funktionalisierung aliphatischer C‐H‐Bindungen

Bietti

2018

Angewandte Chemie

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Die selektive Funktionalisierung nichtaktivierter aliphatischer C‐H‐Bindungen ist ein wichtiges Ziel der modernen Synthesechemie. Jedoch stellt die hochselektive Unterscheidung zwischen Bindungen in organischen Molekülen eine entscheidende Herausforderung dar, und ein tiefgreifendes Verständnis der selbst geringsten Reaktivitätstrends ist unerlässlich. Von den dafür entwickelten Methoden fanden Ansätze basierend auf Wasserstoffatomtransfer (HAT) besonderes Interesse. Dabei wurden Effekte von Reaktionsmedien erfolgreich zur Veränderung der Reaktivität und Regioselektivität in synthetisch bedeutenden C‐H‐Funktionalisierungreaktionen genutzt. In diesem Aufsatz werden die mechanistischen Besonderheiten dieser verfügbaren Strategien diskutiert. Es wird gezeigt, dass Wasserstoffbrücken und Säure‐Base‐Wechselwirkungen die Aktivierung oder Deaktivierung von C‐H‐Bindungen für HAT‐Reagenzien begünstigen und damit zur Feineinstellung von Regioselektivität und Chemoselektivität sowie als Orientierung für zukünftige Entwicklungen und Anwendungen genutzt werden können.

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“…Such approaches open up new avenues for medicinal chemistry to increase the potential of three-dimensional biologically active entities. The Renaud group described a radical cascade reaction for the preparation of pyrrolidine derivatives, using thiyl radical addition to a terminal alkyne function as the first step, which was followed by a 1,5-hydrogen transfer, translocating the radical center for the subsequent cyclization to afford the heterocyclic ring [126]. The Herrera group demonstrated that normally hard to functionalize methyl groups can be easily activated for cyclizations to pyrrolidines by the iodine/iodobenzene diacetate reagent system [127].…”

Section: Working Group 4: Bio-inspired Synthetic Strategiesmentioning

confidence: 99%

COST Action CM1201 “Biomimetic Radical Chemistry”: free radical chemistry successfully meets many disciplines

Ferreri

Golding

Jahn

et al. 2016

Free Radical Research

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The COST Action CM1201 "Biomimetic Radical Chemistry" has been active since December 2012 for 4 years, developing research topics organized into four working groups: WG1 -Radical Enzymes, WG2 -Models of DNA damage and consequences, WG3 -Membrane stress, signalling and defenses, and WG4 -Bio-inspired synthetic strategies. International collaborations have been established among the participating 80 research groups with brilliant interdisciplinary achievements. Free radical research with a biomimetic approach has been realized in the COST Action and are summarized in this overview by the four WG leaders. ARTICLE HISTORY

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Effect of Brønsted acids on the thiophenol-mediated radical addition–translocation–cyclization process for the preparation of pyrrolidine derivatives

Cited by 9 publications

References 34 publications

Activation and Deactivation Strategies Promoted by Medium Effects for Selective Aliphatic C−H Bond Functionalization

Activation and Deactivation Strategies Promoted by Medium Effects for Selective Aliphatic C−H Bond Functionalization

Anwendung von Mediumeffekten in Aktivierungs‐ und Deaktivierungsstrategien zur selektiven Funktionalisierung aliphatischer C‐H‐Bindungen

COST Action CM1201 “Biomimetic Radical Chemistry”: free radical chemistry successfully meets many disciplines

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