Recent advance in direct sp3 carbon-hydrogen bond functionalizations

Abstract

Direct and selective carbon-hydrogen bond functionalization has attracted enormous attention because it provides more efficient strategies for preparing valuable functional molecules from easily available substrates. Significant and exciting developments in functionalization of un-activation Csp 3-H bonds have continuously been made over the past few decades. This review mainly summarizes recent advances on direct Csp 3-H bond functionalization for the formation of CC and C-heteroatom bond under transition-metalcatalysed and metal-free conditions.

Computational Study of Methane C–H Activation by Main Group and Mixed Main Group–Transition Metal Complexes

“…Much effort is invested into researching this reaction in order to convert light alkanes, like methane, to higher-value products for industrial uses [1,2]. There are many well-known challenges to C-H activation, however, as these light alkanes prove to be highly inert and thermodynamically stable [3]. Because of this, computational methods can be very useful in being able to quickly identify novel systems that show promise in being able to activate methane, and which may then be worthy of experimental trials.…”

5d Metal(IV) Imide Complexes. The Impact (or Lack Thereof) of d-Orbital Occupation on Methane Activation and Functionalization

“…1 The main challenge lies in the C−H bonds of light alkanes, which are notoriously inert. 2 Reagents powerful enough to activate these aliphatic C−H bonds are also easily capable of further reacting with the products of the initial reactions, thus limiting selectivity. 3 Carbon−nitrogen bonds are important for applications such as medicine, pharmacology, and polymer synthesis.…”

“…A catalytic method for selectively functionalizing a methane C–H bond and yielding a product that retains a significant portion of the energy from its C–H bonds that also yields a more easily transportable liquid would be of immense economic and environmental benefit . The main challenge lies in the C–H bonds of light alkanes, which are notoriously inert . Reagents powerful enough to activate these aliphatic C–H bonds are also easily capable of further reacting with the products of the initial reactions, thus limiting selectivity .…”

“…Through the use of density functional theory, potential reaction mechanisms for methane activation and functionalization were compared and low-energy pathways discovered. On the basis of literature precedent, ,,− three primary transition states/reaction pathways were tested: oxidative addition, [2+2] addition, and hydrogen atom abstraction (Figure ). Of particular interest is the fact that the mechanisms entail activation directed at the metal, metal–ligand, and ligand portion, respectively, of the complex active site.…”