RESUMEN
The term "C-H functionalisation" incorporates C-H activation followed by its transformation. In a single line, this can be defined as the conversion of carbon-hydrogen bonds into carbon-carbon or carbon-heteroatom bonds. The catalytic functionalisation of C-H bonds using transition metals has emerged as an atom-economical technique to engender new bonds without activated precursors which can be considered as a major drawback while attempting large-scale synthesis. Replacing the transition-metal-catalysed approach with a metal-free strategy significantly offers an alternative route that is not only inexpensive but also environmentally benign to functionalize C-H bonds. Recently metal free synthetic approaches have been flourishing to functionalize C-H bonds, motivated by the search for greener, cost-effective, and non-toxic catalysts. In this review, we will highlight the comprehensive and up-to-date discussion on recent examples of ground-breaking research on green and sustainable metal-free C-H bond functionalisation.
RESUMEN
exo-Metallacycles have become the key reaction intermediates in activating various remote C(sp2)-H and C(sp3)-H bonds in the past decade and aided in achieving unusual site-selectivity. Various novel exo-chelating auxiliaries have assisted metals to reach desired remote C-H bonds of different alcohol and amine-derived substrates. As a result, a wide range of organic transformations of C-H bonds like halogenation, acetoxylation, amidation, sulfonylation, olefination, acylation, arylation, etc. were accessible using the exo-metallacycle strategy. In this review, we have summarized the developments in C-H bond activation via four-, five-, six-, seven- and eight-membered exo-metallacycles and the key reaction intermediates, including the mechanistic aspects, are discussed concisely.
RESUMEN
Storing and transferring electrons for multi-electron reduction processes are considered to be the key steps in various important chemical and biological transformations. In this work, we accomplished multi-electron reduction of a carboxylic acid via a hydrosilylation pathway where a redox-active phenalenyl backbone in Co(PLY-O,O)2(THF)2, stores electrons and plays a preponderant role in the entire process. This reduction proceeds by single electron transfer (SET) from the mono-reduced ligand backbone leading to the cleavage of the Si-H bond. Several important intermediates along the catalytic reduction reaction have been isolated and well characterized to prove that the redox equivalent is stored in the form of a C-H bond in the PLY backbone via a ligand dearomatization process. The ligand's extensive participation in storing a hydride equivalent has been conclusively elucidated via a deuterium labelling experiment. This is a rare example where the ligand orchestrates the multielectron reduction process leaving only the metal to maintain the conformational requirements and fine tunes the electronics of the catalyst.
RESUMEN
An abnormal N-heterocyclic carbene (aNHC) based potassium complex was used as a transition metal-free catalyst for reduction of primary amides to corresponding primary amines under ambient conditions. Only 2 mol% loading of the catalyst exhibits a broad substrate scope including aromatic, aliphatic and heterocyclic primary amides with excellent functional group tolerance. This method was applicable for reduction of chiral amides and utilized for the synthesis of pharmaceutically valuable precursors on a gram scale. During mechanistic investigation, several intermediates were isolated and characterized through spectroscopic techniques and one of the catalytic intermediates was characterized through single-crystal XRD. A well-defined catalyst and isolable intermediate along with several stoichiometric experiments, in situ NMR experiments and the DFT study helped us to sketch the mechanistic pathway for this reduction process unravelling the dual role of the catalyst involving nucleophilic activation by aNHC along with Lewis acidic activation by K ions.
