Xanthate-Mediated Incorporation of Quaternary Centers into Heteroarenes

Revil-Baudard, Vincent L.; Vors, Jean‐Pierre; Zard, Samir Z.

doi:10.1021/acs.orglett.8b01299

Cited by 33 publications

(16 citation statements)

References 41 publications

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“…Although interesting, this transformation was, however, only moderately efficient with pyridine derivatives. The same authors also described the use of other xanthates for the addition of tertiary alkyl radicals to several electron‐deficient heteroarenes (as well as to some azoles and indoles) and for the aminomethylation of pyrazines …”

Section: Alkylation Of Heteroarenesmentioning

confidence: 99%

Beyond Friedel and Crafts: Innate Alkylation of C−H Bonds in Arenes

Evano

Theunissen

2019

Angew Chem Int Ed

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Alkylated arenes are ubiquitous molecules and building blocks commonly utilized in most areas of science where there is a need for small organic molecules. Despite its apparent simplicity, the regioselective alkylation of arenes is still a challenging transformation in a lot of cases. Classical methods for the introduction of alkyl groups on arenes, which include the venerable Friedel-Crafts reaction, radical additions, metallation or pre-functionalization of the arene, as well as alternatives such as the directed alkylation of C-H bonds, still suffer from severe limitations in terms of scope, efficiency and selectivity. This can be addressed by exploiting the innate reactivity of some (hetero)arenes, in which electronic and steric properties, governed (or not) by the presence of one (or multiple) heteroatom(s) ensure high levels of regioselectivity. These innate alkylations of C-H bonds in (hetero)arenes will be overviewed, in a comprehensive manner, in this review article.

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Section: Alkylation Of Heteroarenesmentioning

confidence: 99%

Beyond Friedel and Crafts: Innate Alkylation of C−H Bonds in Arenes

Evano

Theunissen

2019

Angew Chem Int Ed

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“…Te rtiary radicals, such as tert-butyl (141 ab,S cheme 29), are sufficiently stabilized and can be incorporated directly,i nc ontrast to less stable primary radicals. [65] Such motifs have to be introduced in al atent form (see the synthesis of compound 34 in Scheme 5). To attach am ethyl or an ethyl group to the indole, as imple method is to introduce first an acetic or pro-pionic acid moiety,a ss hown for compounds 141 ac and 141 ae,b yr eacting ethyl 3-indolecarboxylate with the corresponding xanthate.…”

Section: Intermolecular Additions To Indolesmentioning

confidence: 99%

The Xanthate Route to Indolines, Indoles, and their Aza Congeners

Zard

2020

Chemistry A European J

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Convergentr outes to av ariety of indolines, indoles, oxindoles, and their aza analogues involving radical additions of xanthates are described. Three approaches are summarized. The first is the least general and relies on the generation of aryl or heteroaryl radicals startingf rom diazonium salts. The second involves radical addition to N-allylanilines followed by ring-closure onto the aromatic core. A large varietyo fi ndolines and azaindolines can thus be obtained and, in many cases, converted into the corresponding indoles and azaindoles by variousm ethods. Thes ynthesiso f novel fluoroazaindolines and fluoroazaindoles by ar are homolytic ipso-substitution of fluorine atoms is particularly noteworthy.T he last approachh inges on the direct modification of indoles by radical addition to the pyrrole subunit of the indolen ucleus. Application of this methodology to the total synthesis of melatonin andt he alkaloids mersicarpine, caulerpine, and the pentacyclic skeleton of tronocarpine is briefly discussed. Mosto ft he compounds described herein would be difficult to obtain by more traditional routes.

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“…Diese interessante Transformation verlief mit Pyridinderivaten allerdings nur mäßig effizient. Dieselben Autoren beschrieben auch die Umsetzung anderer Xanthogenate für die Addition tertiärer Alkylradikale an mehrere elektronenarme Heteroarene (sowie einige Azole und Indole) und für die Aminomethylierung von Pyrazinen …”

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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Xanthate-Mediated Incorporation of Quaternary Centers into Heteroarenes

Cited by 33 publications

References 41 publications

Beyond Friedel and Crafts: Innate Alkylation of C−H Bonds in Arenes

Beyond Friedel and Crafts: Innate Alkylation of C−H Bonds in Arenes

The Xanthate Route to Indolines, Indoles, and their Aza Congeners

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

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