Iron-Catalyzed C–H Bond Activation

Abstract

Catalytic C-H bond activation, which was an elusive subject of chemical research until the 1990s, has now become a standard synthetic method for the formation of new C-C and C-heteroatom bonds. The synthetic potential of C-H activation was first described for ruthenium catalysis and is now widely exploited by the use of various precious metals. Driven by the increasing interest in chemical utilization of ubiquitous metals that are abundant and nontoxic, iron catalysis has become a rapidly growing area of research, and iron-catalyzed C-H activation has been most actively explored in recent years. In this review, we summarize the development of stoichiometric C-H activation, which has a long history, and catalytic C-H functionalization, which emerged about 10 years ago. We focus in this review on reactions that take place via reactive organoiron intermediates, and we excluded those that use iron as a Lewis acid or radical initiator. The contents of this review are categorized by the type of C-H bond cleaved and the type of bond formed thereafter, and it covers the reactions of simple substrates and substrates possessing a directing group that anchors the catalyst to the substrate, providing an overview of iron-mediated and iron-catalyzed C-H activation reported in the literature by October 2016.

Jenseits von Friedel und Crafts: dirigierte Alkylierung von C‐H‐Bindungen in Arenen

“…[34] Tatsächlich katalysiert ein einfacher Eisenkomplex, Fe-(PMe 3 ) 4 ,effizient die selektive Alkylierung von Arylketonen mit einer großen Auswahl an Alkenen, einschließlich aryl-, alkyl-, silyl-sowie sauerstoff-und stickstoffsubstituierten Alkenen, die alle mit hervorragenden Selektivitäten die linearen Produkte ergeben, wie von Kakiuchi et al berichtet wurde (Schema 5). [34] Tatsächlich katalysiert ein einfacher Eisenkomplex, Fe-(PMe 3 ) 4 ,effizient die selektive Alkylierung von Arylketonen mit einer großen Auswahl an Alkenen, einschließlich aryl-, alkyl-, silyl-sowie sauerstoff-und stickstoffsubstituierten Alkenen, die alle mit hervorragenden Selektivitäten die linearen Produkte ergeben, wie von Kakiuchi et al berichtet wurde (Schema 5).…”

Hydroarylations by cobalt-catalyzed C–H activation

“…A wide range of transition metal-catalyzed non-directed or directing group assisted C–H activation methodologies have been developed to build new C–X (X = carbon or heteroatom) bonds [7–10] and they offer efficient routes to the synthesis of natural products, materials, agrochemicals, polymers, and pharmaceuticals [11–15]. Specifically, the first-row transition metal catalysts, which are less expensive and more environmentally benign, have attracted significant attention in recent years [16–27]. As a member of the first-row transition metals, cobalt complexes are known to be extensively involved in homogeneous catalysis, in particular, C–H activation.…”

Three‐Dimensional Heterocycles by Iron‐Catalyzed Ring‐Closing Sulfoxide Imidation

“…[8] Its use in catalyzed nitrene transfer reactions has led to convenient methods for C À H bond aminations. [8] Its use in catalyzed nitrene transfer reactions has led to convenient methods for C À H bond aminations.…”