Advances in Group 10 Transition-Metal-Catalyzed Arene Alkylation and Alkenylation

Abstract

On a large scale, the dominant method to produce alkyl arenes has been arene alkylation from arenes and olefins using acid-based catalysis. The addition of arene C−H bonds across olefin CC bonds catalyzed by transition-metal complexes through C−H activation and olefin insertion into metal−aryl bonds provides an alternative approach with potential advantages. This Perspective presents recent developments of olefin hydroarylation and oxidative olefin hydroarylation catalyzed by molecular complexes based on group 10 transition metals (Ni, Pd, Pt). Emphasis is placed on comparisons between Pt catalysts and other group 10 metal catalysts as well as Ru, Ir, and Rh catalysts.

Continuous Flow Preparation of Benzylic Sodium Organometallics

“…Compared to their branched counterparts they are easily biodegradable and therefore more environmentally friendly. However, the installation of the linear alkyl chain can be challenging as cationic methods often lead to branched structures [18, 36] . As we showed earlier, the introduction of linear alkyl chain using our Wurtz‐type procedure is uncomplicated and high yielding.…”

Herstellung von benzylischen Natrium‐Metallorganylen im kontinuierlichen Durchfluss

“…Im Vergleich zu ihren verzweigten Gegenstücken sind sie leichter biologisch abbaubar und daher umweltfreundlicher. Der Einbau der linearen Alkylkette kann jedoch eine Herausforderung darstellen, da kationische Methoden häufig zu verzweigten Strukturen führen [18, 36] . Wie wir bereits gezeigt haben, ist die Einführung der linearen Alkylkette mit unserem Wurtz‐Typ‐Verfahren unkompliziert und führt zu hohen Ausbeuten.…”

Half‐Sandwich (η6‐Benzene)Ruthenium(II) Complex of Picolyl Functionalized N‐Heterocyclic Carbene as an Efficient Catalyst for Thioether Directed C−H Alkenylation of Arenes

“…Knowing the high catalytic potential of Ru complexes, [27] and in the mindset to search a feasible methodology, a half-sandwich Ru(II) complex of picolyl-functionalized N-heterocyclic carbene was synthesized and catalytically explored for the thioether directed CÀ H alkenylation of arenes (Scheme 4). The Ru-catalyst along with copper acetate (co-catalyst) is efficiently working at the mild conditions for broad varieties of substrates.…”

“…1-(2-Chloroethyl)-1H-benzimidazole (a) and 1-(2-(phenylthio)ethyl)-1H-benzimidazole (b) were synthesized by using a previously reported procedure. [27] In the next step, the atom economy reaction of (2bromomethyl)pyridine with 1-(2-(phenylthio)ethyl)-1H-benzimidazole resulted in N-(1-thiophenyl-2-ethyl)-N'-(pyridine-2ylmethyl)benzimidazolium bromide (c). Thereafter, the Ru(II) complex was synthesized by employing a silver carbene transfer reaction in which c was first treated in CH 2 Cl 2 with Ag 2 O in a N 2 atmosphere at room temperature (in dark), followed by the addition of a methanol suspension of [η 6 (C 6 H 6 )RuCl(μ-Cl)] 2 .…”