DPPF-Catalyzed Atom-Transfer Radical Cyclization via Allylic Radical

Hou, Longlei; Zhou, Zhao‐Zhao; Wang, Dong; Zhang, Kun; Chen, Xin; Zhou, Li-Jin; Yang, Hong; Liu, Wei; Hou, Yading; Tong, Xiaofeng

doi:10.1021/acs.orglett.7b03135

Cited by 23 publications

(16 citation statements)

References 40 publications

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“…For an excellent overview on iron‐catalyzed cross‐couplings involving radical intermediates, we refer to a Review published by Jahn . It is important to mention that Fe complexes are also known to catalyze atom‐transfer radical additions (ATRA) and Kharasch‐type additions . In analogy to manganese (see Section 4.4), iron can mediate C−H hydroxylations, halogenations, and azidations…”

Section: Radical–metal Crossover Reactionsmentioning

confidence: 99%

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The Persistent Radical Effect in Organic Synthesis

2019

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Radical–radical couplings are mostly nearly diffusion‐controlled processes. Therefore, the selective cross‐coupling of two different radicals is challenging and not a synthetically valuable transformation. However, if the radicals have different lifetimes and if they are generated at equal rates, cross‐coupling will become the dominant process. This high cross‐selectivity is based on a kinetic phenomenon called the persistent radical effect (PRE). In this Review, an explanation of the PRE supported by simulations of simple model systems is provided. Radical stabilities are discussed within the context of their lifetimes, and various examples of PRE‐mediated radical–radical couplings in synthesis are summarized. It is shown that the PRE is not restricted to the coupling of a persistent with a transient radical. If one coupling partner is longer‐lived than the other transient radical, the PRE operates and high cross‐selectivity is achieved. This important point expands the scope of PRE‐mediated radical chemistry. The Review is divided into two parts, namely 1) the coupling of persistent or longer‐lived organic radicals and 2) “radical–metal crossover reactions”; here, metal‐centered radical species and more generally longer‐lived transition‐metal complexes that are able to react with radicals are discussed—a field that has flourished recently.

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Section: Radical–metal Crossover Reactionsmentioning

confidence: 99%

“…[153,154] c) Fe-catalyzed CÀCcross-coupling comprising aradical 1,5-HAT. [156] Angewandte Chemie Reviews catalyze atom-transfer radical additions (ATRA) [121,157] and Kharasch-type additions. [158] In analogy to manganese (see Section 4.4), iron can mediate C À Hhydroxylations,halogenations,and azidations.…”

Section: Ironmentioning

confidence: 99%

The Persistent Radical Effect in Organic Synthesis

2019

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“…Several control experiments further confirmed the involvement of radical pathway in this cycloisomerization process (Scheme 34). [52] In 2018, Li, Bao and co-workers discovered a Fecatalyzed radically initiated intermolecular carboiodination reaction of terminal alkynes with secondary alkyl iodides for the synthesis of synthetically valuable vinyl iodides. Thorough screening of the reaction conditions revealed utilization of 10 mol% Fe(OTf) 3 along with 1 equiv.…”

Section: Fe-catalyzed 12-difunctionalizationsmentioning

confidence: 99%

Transition‐Metal‐Catalyzed Carbohalogenative 1,2‐Difunctionalization of C−C Multiple Bonds

2020

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Transition-metal-catalyzed 1,2-carbohalofunctionalization reactions of CÀ C multiple bonds have emerged rapidly over the past decade as a powerful tool for generating a new carbon-carbon and carbon-halogen bond via transposition of an existing carbon-halogen σ bond. Exploring this highly efficient mode of carbon-carbon multiple bond difunctionalization, various research groups have established novel strategies for the synthesis of organohalides by utilizing wide variety of transition metal catalysts under mild reaction conditions, avoiding stoichiometric waste of by-products, and with improved levels of chemo-, regio-, and stereoselectivities. Most of the 1,2-carbohalo-functionalization reactions involve either the carbon-halogen reductive elimination mechanism or the atom transfer radical addition (ATRA) mechanism. This review summarizes the recent progress in the area of transitionmetal-catalyzed intra-and intermolecular 1,2-carbo-halo-functionalization reactions of carbon-carbon multiple bonds and explicates the underlying potentiality and challenges within the field.

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“…Für einen detaillierteren Einblick in Eisen‐katalysierte Kreuzkupplungen mit radikalischen Intermediaten verweisen wir auf einen von Jahn veröffentlichten Übersichtsartikel . Es ist erwähnenswert, dass Eisen‐Komplexe auch dafür bekannt sind, Atomtransfer‐Radikaladditionen und Kharasch‐artige Additionen einzugehen. In Analogie zu Mangan (siehe Abschnitt 4.4) kann Eisen zudem auch C‐H‐Hydroxylierungen, ‐Halogenierungen und Azidierungen vermitteln…”

Section: Radikal‐metall‐kreuzungsreaktionenunclassified

Der “Persistent Radical Effect” in der organischen Chemie

2019

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Radikal‐Radikal‐Kupplungen sind nahezu diffusionskontrollierte Prozesse. Daher sind selektive Kreuzkupplungen zweier unterschiedlicher Radikale schwierig zu realisieren und stellen somit synthetisch nicht wertvolle Prozesse dar. Wenn die beiden Radikale allerdings eine unterschiedliche Lebensdauer aufweisen und in gleichen Raten gebildet werden, wird die Kreuzkupplung zum dominierenden Prozess. Die hohe Kreuzselektivität basiert auf einem kinetischen Phänomen, dem “Persistent Radical Effect” (PRE). In diesem Aufsatz wird eine von Simulationen einfacher Modellsysteme gestützte Erklärung des PRE geliefert. Weiter werden die Stabilität von Radikalen in Bezug auf ihre Lebensdauer und verschiedene Beispiele für PRE‐vermittelte Radikal‐Radikal‐Kupplungen in der Synthese diskutiert. Es wird gezeigt, dass der PRE nicht auf Kupplungen persistenter mit transienten Radikalen beschränkt ist. Der PRE mit einhergehender hoher Kreuzselektivität greift bereits, wenn ein Kupplungspartner langlebiger als das andere transiente Radikal ist. Diese Tatsache erweitert signifikant das Anwendungsgebiet PRE‐vermittelter Radikalchemie. Dieser Aufsatz ist in zwei Teile aufgeteilt: 1) die Kupplung persistenter oder langlebiger organischer Radikale und 2) Radikal‐Metall‐Kreuzungsreaktionen; hierbei werden Metall‐zentrierte Radikalspezies oder allgemeiner langlebige Übergangsmetallkomplexe, welche mit Radikalen reagieren, diskutiert – ein Gebiet, das jüngst stark expandiert ist.

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DPPF-Catalyzed Atom-Transfer Radical Cyclization via Allylic Radical

Cited by 23 publications

References 40 publications

The Persistent Radical Effect in Organic Synthesis

The Persistent Radical Effect in Organic Synthesis

Transition‐Metal‐Catalyzed Carbohalogenative 1,2‐Difunctionalization of C−C Multiple Bonds

Der “Persistent Radical Effect” in der organischen Chemie

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