Iron-Catalyzed Homocoupling of Aryl Halides and Derivatives in the Presence of Alkyllithiums

Abstract

Direct synthesis of biaryl derivatives from aryl halides takes place under very mild temperature conditions by using a ligand-free iron catalytic system. The procedure, which proceeds via an in situ quantitative aryl halide exchange with alkyllithiums, allows for excellent control of the reactivity and is in line with the sustainable development. The method is also applicable to styryl and benzyl halides and to phenylacetylene.

Iron Catalysis in Organic Synthesis

“…Taillefer et al described an iron-catalyzed homocoupling of aryl halides in the presence of alkyllithium reagents (Scheme 229). 457 Iron(II) chloride was applied as catalyst and triethylamine was applied as additive. This procedure afforded a variety of biaryls in good to excellent yields.…”

Mechanism and Applications of the Photoredox Catalytic Coupling of Benzyl Bromides

“…[1][2][3] The discoveryo ft he biological actions of dihydrostilbenoids, such as those of the combretastatin series, [4] have sparkedr enewed research interest in the synthesis of bibenzyl derivatives. The catalytic mechanism involves the oxidative addition of benzyl halides into low-valent complexes of Mn, [8,14,[25][26][27] Fe, [9,10,28] Ni, [20,22,29] Cu, [16-18, 30, 31] V, [32] Rh, [33] In, [34] Ti, [15,35] and Sm [36,37] that can be generated in the presence of electrons ourcesw ith very negative oxidationp otentials. To expand syntheticr outes to bibenzyls, novel methods that promote the Csp 3 -Csp 3 coupling of halomethyl arenes have been developed.…”

Palladium‐Catalyzed, tert‐Butyllithium‐Mediated Dimerization of Aryl Halides and Its Application in the Atropselective Total Synthesis of Mastigophorene A

“…[23] This compound was synthesized by starting with the palladium-catalyzed asymmetric conjugate addition of aryl boronic acid 6 to pentenone 5 to give compound 7 (46 %y ield, 92 % ee). [24] Geminal dimethylation and subsequent removal of the enone functionality (thioenone formation and reduction with Raney Ni) [21] gave rise to dimethylherbertenediol (10) in 56 %over the three steps.Subsequently, 10 was brominated to furnish 11,thus setting the stage for the pivotal homocoupling. [24] Geminal dimethylation and subsequent removal of the enone functionality (thioenone formation and reduction with Raney Ni) [21] gave rise to dimethylherbertenediol (10) in 56 %over the three steps.Subsequently, 10 was brominated to furnish 11,thus setting the stage for the pivotal homocoupling.…”

“…[8][9][10][11][12] Themethodologies reported so far were rather limited in their scope and did not involve the construction of sterically congested tetra-ortho-substituted biaryl compounds,e xcept for three examples of ac opper-mediated coupling reported by Spring and co-workers. [8][9][10][11][12] Themethodologies reported so far were rather limited in their scope and did not involve the construction of sterically congested tetra-ortho-substituted biaryl compounds,e xcept for three examples of ac opper-mediated coupling reported by Spring and co-workers.…”

“…Despite important recent advances,t he homocoupling of organolithium reagents under Pd catalysis has received little attention. [8][9][10][11][12] Themethodologies reported so far were rather limited in their scope and did not involve the construction of sterically congested tetra-ortho-substituted biaryl compounds,e xcept for three examples of ac opper-mediated coupling reported by Spring and co-workers. [8] Furthermore, the application of this type of coupling methodology in the synthesis of biaryl-containing natural products has not been reported.…”