Iron‐Catalyzed Alkyl–Alkyl Suzuki–Miyaura Coupling

Hatakeyama, Takuji; Hashimoto, Toru; Kathriarachchi, Kalum K. A. D. S.; Zenmyo, Takeshi; Seike, Hirofumi; Nakamura, Masaharu

doi:10.1002/anie.201202797

Cited by 181 publications

(105 citation statements)

References 71 publications

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“…The role of cosolvents or additives is still not really well understood. Also, the employment of nucleophiles beyond Grignard reagents (e.g., based on zinc or boron) needs to be further pursued, and efforts in this direction appeared recently in the literature [48,49]. Finally, further mechanistic investigations are necessary, as little is currently known concerning the nature (and especially the oxidation state) of the catalytically active iron species.…”

Section: C-c Bond-forming Reactionsmentioning

confidence: 97%

Iron Catalysis: Historic Overview and Current Trends

Bauer

2015

Topics in Organometallic Chemistry

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Iron catalysis is a growing area of research, as seen by an exponential increase in the publication activities on the topic. This introductory chapter provides a historic overview of the development of iron catalysis including some notable milestones. The advantages of iron, i.e., its abundance, low price, and relative nontoxicity, are discussed, and an overview of the main type of reactions catalyzed by iron is outlined. The advances of heterogeneous iron catalysis (which is not covered in this volume) are exemplified with a few notable cases. Finally, the potential impact of metal impurities in iron sources on the catalytic activity is discussed.

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Section: C-c Bond-forming Reactionsmentioning

confidence: 97%

Iron Catalysis: Historic Overview and Current Trends

Bauer

2015

Topics in Organometallic Chemistry

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“…[151] It was later experimentally shown that an iron(I) complex is ac ompetent catalyst for such cross-couplings. [152] Based on computational studies,t he groups of Gutierrez [153] and Nakamura and Morokuma [154] independently proposed two slightly different mechanisms for such iron cross-couplings.It was suggested in both cases that an iron(I) species first reductively cleaves the alkyl halide (Figure 31 b, step A) to give an iron(II) intermediate and aC radical. TheF e II complex is able to trap the transient alkyl radical (step C) to generate an iron(III) complex, which then undergoes reductive elimination (step D) to liberate the coupling product, thereby regenerating the starting iron(I) species.…”

Section: Ironmentioning

confidence: 99%

“…Theo nly difference between the two suggested catalytic cycles lies in the transmetalation step (step B). Theg roup of Gutierrez [153] proposed the transmetalation with the iron(I) complex whereas Nakamura and Morokuma [154] suggested that step to occur at the iron(II) oxidation state.Returning to the PRE, in both proposals,atransient Cradical and alongerlived metal species are generated at the same rate in step A. Theselective cross-coupling of both intermediates is based on the accumulation of the longer-lived (with respect to the transient alkyl radical) iron(II) complex.…”

Section: Ironmentioning

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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“…Their work pushed iron cross-coupling towards its current, highly productive state, broadening the substrate scope of Fe cross-couplings while highlighting the sensitivity of the reactivities of Fe(II) and Fe(III) salts to additives, such as NMP. [12] More recently, reaction additives (TMEDA, [13–15] NHCs [16–21] , bisphosphines [20,22–25] ) and well-defined mononuclear iron complexes have been employed to generate more robust cross-coupling systems with a broad substrate scope in Kumada, Negishi and Suzuki-Miyaura type cross-couplings. Additionally, studies by Fürstner and coworkers, as well as Hayashi and Nagano, explored the scope of Grignard reagents and electrophiles that can be utilized in iron-catalzed cross-coupling reactions.…”

Section: Introductionmentioning

confidence: 99%

A Physical‐Inorganic Approach for the Elucidation of Active Iron Species and Mechanism in Iron‐Catalyzed Cross‐Coupling

Carpenter

Neidig

2017

Israel Journal of Chemistry

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Detailed studies of iron speciation and mechanism in iron-catalyzed cross-coupling reactions are critical for providing the necessary fundamental insight to drive new reaction development. However, such insight is challenging to obtain due to the prevalence of mixtures of unstable, paramagnetic organoiron species that can form in this chemistry. A physical-inorganic research approach combining freeze-trapped inorganic spectroscopic studies, organometallic synthesis and GC/kinetic studies provides a powerful method for studying such systems. Mössbauer, EPR and MCD spectroscopy enable the direct investigation of in situ formed iron species and, combined with GC analysis, the direct correlation of reactions of specific iron species to the generation of organic products. This review focuses on a description of the key methods involved in this physical-inorganic approach, as well as examples of its application to investigations of iron-SciOPP catalyzed cross-coupling catalysis.

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Iron‐Catalyzed Alkyl–Alkyl Suzuki–Miyaura Coupling

Cited by 181 publications

References 71 publications

Iron Catalysis: Historic Overview and Current Trends

Iron Catalysis: Historic Overview and Current Trends

The Persistent Radical Effect in Organic Synthesis

A Physical‐Inorganic Approach for the Elucidation of Active Iron Species and Mechanism in Iron‐Catalyzed Cross‐Coupling

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