Domino Iron Catalysis: Direct Aryl–Alkyl Cross‐Coupling

Czaplik, Waldemar Maximilian; Mayer, Michael; Wangelin, Axel Jacobi von

doi:10.1002/anie.200804434

Cited by 249 publications

(80 citation statements)

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“…In 2009, Von Wangelin and Lipshultz independently published Fe-and Pdcatalyzed in situ Kumada and Negishi coupling of alkyl and aryl halides (Scheme 13) [41,42]. Both methods merit faster formation of alkyl magnesium and zinc reagents than aryl ones when exposure to Mg or Zn.…”

Section: Ni-catalyzed Reductive Arylation Of Alkyl Halidesmentioning

confidence: 97%

Nickel-Catalyzed Reductive Couplings

2016

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The Ni-catalyzed reductive coupling of alkyl/aryl with other electrophiles has evolved to be an important protocol for the construction of C-C bonds. This chapter first emphasizes the recent progress on the Ni-catalyzed alkylation, arylation/vinylation, and acylation of alkyl electrophiles. A brief overview of CO2 fixation is also addressed. The chemoselectivity between the electrophiles and the reactivity of the alkyl substrates will be detailed on the basis of different Ni-catalyzed conditions and mechanistic perspective. The asymmetric formation of C(sp(3))-C(sp(2)) bonds arising from activated alkyl halides is next depicted followed by allylic carbonylation. Finally, the coupling of aryl halides with other C(sp(2))-electrophiles is detailed at the end of this chapter.

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Section: Ni-catalyzed Reductive Arylation Of Alkyl Halidesmentioning

confidence: 97%

Nickel-Catalyzed Reductive Couplings

2016

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“…Good yields of cross-coupled products were obtained. 50 There has been a great deal of activity in the areas of Grignard reagent/organic halide cross-coupling and aryl Grignard reagent homocoupling, and the coverage in this essay, whose focus is on the historical aspects, is far from exhaustive. Attention is called to the 2005 review by Frisch and Beller 51 and especially to the recent Accounts of Chemical Research special issue on cross-coupling.…”

Section: Scheme 3 Schemementioning

confidence: 99%

The Grignard Reagents

2009

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During the past 100 years the Grignard reagents probably have been the most widely used organometallic reagents. Most of them are easily prepared in ethereal solution (usually diethyl ether or, since the early 1950s, THF) by the reaction of an organic halide with metallic magnesium (eq 1).Most of them are stable in ethereal solution (although atmospheric moisture and oxygen should be excluded) and in general are quite reactive. Discovered by Victor Grignard at the University of Lyon in France in 1900, 1 their ease of preparation and their broad applications in organic and organometallic synthesis made these new organomagnesium reagents an instant success. The importance of this contribution to synthetic chemistry was recognized very early, and for his discovery Grignard was awarded a Nobel Prize in Chemistry in 1912.Our cover molecule is the monomeric ethylmagnesium bromide bis(diethyl etherate) (1), whose solid-state molecular structure was determined by an X-ray diffraction study by Lloyd Guggenberger and Robert Rundle in 1964 using crystals isolated from a diethyl ether solution of a C 2 H 5 Br/Mg reaction mixture by slow cooling with a stream of cold gaseous nitrogen. 2-4Generally written as "RMgX" in textbooks, monographs and research papers, the Grignard reagents in ethereal solution are more complicated than this simple formula indicates. As Wilhelm Schlenk and his son discovered 80 years ago, more than one magnesium-containing species exists in the diethyl ether solution of a Grignard reagent.5 A redistribution of the substituents on magnesium takes place, and the RMgX species ends up in equilibrium with the two symmetrical species, the diorganomagnesium and the magnesium dihalide: the "Schlenk Equilibrium" (eq 2). 5The species that contain Mg-halogen bonds can be precipitated from Grignard reagent solutions in diethyl ether by the addition of 1,4-dioxane. An insoluble, polymeric 1,4-dioxane adduct is formed, leaving behind a solution of R 2 Mg 5 sa useful preparation of dialkyl-and diarylmagnesium reagents.6 Wilhelm Schlenk, Jr. analyzed the 1,4-dioxane precipitations from a number of Grignard reagent solutions. 7 Assuming that the precipitation is essentially instantaneous, i.e., that the calculated R 2 Mg, MgX 2 , and RMgX percentages reflect the actual composition of the Grignard reagent solution at equilibrium, Schlenk reported the compositions collected in (6) (a) Cope, A. C. J. Am. Chem. Soc. 1935, 57, 2238 As Erwin Weiss found, evaporation of diethyl ether solutions of methyl-and ethylmagnesium bromide and chloride at reduced pressure followed by heating of the colorless solid residues at ca. 100°C and 0.001 mmHg for several hours gave a mixture of the respective pure, solvent-free, polymeric R 2 Mg compounds and magnesium halides. The solid MgCl 2 thus obtained differed from a sample obtained from a MgCl 2 melt in that its lattice showed a strong stacking disorder. This form of MgCl 2 had an extremely high surface area: Weiss, E.

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“…Our first suspicion was that iron or other metals from the stainless steel system were catalyzing the coupling, a well known catalytic reaction [4]. We immediately converted to an all glass and fluoropolymer system consisting of Fisher-Porter style glass pressure flasks with PTFE clad stir bars, FEP transfer tubes and PFA valves [5].…”

Section: *Manuscriptmentioning

confidence: 99%

Addition reactions of organometallic reagents to nitrogen trifluoride and enhanced alkyl–alkyl coupling by NF3

Belter

2015

Journal of Fluorine Chemistry

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Domino Iron Catalysis: Direct Aryl–Alkyl Cross‐Coupling

Cited by 249 publications

References 53 publications

Nickel-Catalyzed Reductive Couplings

Nickel-Catalyzed Reductive Couplings

The Grignard Reagents

Addition reactions of organometallic reagents to nitrogen trifluoride and enhanced alkyl–alkyl coupling by NF3

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