C–H activation has surfaced as an increasingly powerful tool for molecular sciences, with notable applications to material sciences, crop protection, drug discovery, and pharmaceutical industries, among others. Despite major advances, the vast majority of these C–H functionalizations required precious 4d or 5d transition metal catalysts. Given the cost-effective and sustainable nature of earth-abundant first row transition metals, the development of less toxic, inexpensive 3d metal catalysts for C–H activation has gained considerable recent momentum as a significantly more environmentally-benign and economically-attractive alternative. Herein, we provide a comprehensive overview on first row transition metal catalysts for C–H activation until summer 2018.

3d Transition Metals for C-H Activation.

ConspectusTraditional organic synthesis relies heavily on the transformations of various preinstalled functional groups, such as cross-coupling reactions using organohalides and organometallic reagents. The strategy of C–H activation enables the direct formation of C–C/C–X (X = heteroatom) bonds from inert C–H bonds, which can enhance the atom- and step-economy of organic synthesis. To date, precious metals have overwhelmingly dominated the C–H activation field; however, the rarity and high cost of these metals necessitate the development of more sustainable catalysts. In this regard, catalysts based on manganese are highly desirable owing to the abundant reserve of manganese in the earth’s crust and its economic benefits, low toxicity, and potentially unique reactivity. Although the first stoichiometric manganese-mediated C–H activation reaction was reported as early as 1970, manganese-catalyzed C–H activation reactions are largely underdeveloped. How to construct an efficient catalytic cycle for mangane...

Inert C-H Bond Transformations Enabled by Organometallic Manganese Catalysis.

Manganese(I)-catalyzed C-H alkynylations with organic halides occurred with unparalleled substrate scope, and thus enabled step-economical C-H functionalizations with silyl, aryl, alkenyl, and alkyl haloalkynes. The versatility of the manganese(I) catalysis manifold enabled C-H couplings with haloalkynes featuring, among others, fluorescent labels, steroids, and amino acids, thereby setting the stage for peptide ligation as well as the efficient molecular assembly of acyclic and cyclic peptides. A plausible catalytic cycle was proposed.

Manganese-Catalyzed C-H Alkynylation: Expedient Peptide Synthesis and Modification.

Earth-abundant metal catalysts are critically needed for sustainable chemical synthesis. Here we report a simple, cheap and effective strategy of producing novel earth-abundant metal catalysts at metal-organic framework (MOF) nodes for broad-scope organic transformations. The straightforward metalation of MOF secondary building units (SBUs) with cobalt and iron salts affords highly active and reusable single-site solid catalysts for a range of organic reactions, including chemoselective borylation, silylation and amination of benzylic C-H bonds, as well as hydrogenation and hydroboration of alkenes and ketones. Our structural, spectroscopic and kinetic studies suggest that chemoselective organic transformations occur on site-isolated, electron-deficient and coordinatively unsaturated metal centres at the SBUs via σ-bond metathesis pathways and as a result of the steric environment around the catalytic site. MOFs thus provide a novel platform for the development of highly active and affordable base metal catalysts for the sustainable synthesis of fine chemicals.

Chemoselective single-site Earth-abundant metal catalysts at metal–organic framework nodes

In industries and academic laboratories, several late transition metal-catalyzed prerequisite reactions are widely performed during single and multistep synthesis. However, besides the desired products, these reactions lead to the generation of numerous chemical waste materials, by-products, hazardous gases, and other poisonous materials, which are discarded in the environment. This is partly responsible for the creation of global warming, resulting in climate adversities. Thus, the development of environmentally benign, cheap, easily accessible, and earth-abundant metal catalysts is desirable to minimize these issues. Certainly, iron is one of the most important metals belonging to this family. The field of iron catalysis has been explored in the last two-three decades out of its rich chemistry depending on its oxidation states and ligand cooperation. Moreover, this field has been enriched by the promising development of iron-catalyzed reactions namely, C–H bond activation, including organometallic C–H activation and C–H functionalization via outer-sphere pathway, cross-dehydrogenative couplings, insertion reactions, cross-coupling reactions, hydrogenations including hydrogen borrowing reactions, hydrosilylation and hydroboration, addition reactions and substitution reactions. Thus, herein an inclusive overview of these reaction have been well documented.

Organic synthesis with the most abundant transition metal–iron: from rust to multitasking catalysts

In the past thirty years, transition metal catalyzed silylation of inert C-H bonds has attracted intensive attention due to the importance and wide use of organosilicon compounds. In this review, the silylation reactions of inert C-H bonds catalyzed by transition metal complexes of Ir, Rh, Ru, Pt, Pd, Ni, and Sc, and the strategies utilized to access the site-selective C-H silylation products have been summarized. Furthermore, the mechanisms of C-H silylation reactions have been discussed briefly.

Direct silylation reactions of inert C-H bonds via transition metal catalysis

Direct Silylation Reactions of Inert C—H Bonds via Transition Metal Catalysis

A manganese-catalyzed bicyclic annulation of imines with α,β-unsaturated esters via C–H activation is described, which provides an expedient access to fused β-lactams in one-step operation with high efficiency and good functional group tolerance. Of note, both ketimines and aldimines are amenable to this transformation. Mechanistic studies have identified a five-membered azamanganacycle as the key reaction intermediate.

Manganese-catalyzed bicyclic annulations of imines and α , β -unsaturated esters via C−H activation

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Direct silylation reactions of inert C-H bonds via transition metal catalysis

Direct Silylation Reactions of Inert C—H Bonds via Transition Metal Catalysis

Manganese-catalyzed bicyclic annulations of imines and α , β -unsaturated esters via C−H activation