This review summarises deuteration methods of various organic motifs containing C(sp2)−H and C(sp3)−H bonds utilizing C−H bond functionalisation as a key step along with a variety of catalysts, and exemplifies their biological relevance.

Nitrile is one of the ubiquitous functional groups in natural products and polymer industry. It is often used as a versatile building block in synthetic chemistry. Classically, nitrile group is used for alpha functionalization, orthoÀ CÀ H activation and as a precursor for amine or carbonyl functionalities. With the development of various transition metal catalyzed methods, in the last two decades, nitrile group has emerged as a source of carbon synthons through CÀ CN bond activation despite of its high bond energy. In this review we have summarized all recent developments involving the carbon synthons arising from the cleavage of CÀ CN bonds. Depending on the fate of the carbon center after cleavage, all the reactions are classified in two major categories for the ease of discussion: 1) decyanation (removal of the nitrile group) and 2) decyanative functionalization (replacement of the nitrile group). Finally, current limitations in CÀ CN bond activation strategies and future prospects are discussed.

Nitroolefins are important synthetic intermediates in the field of organic synthesis as well as in medicinal chemistry. The high reactivity of nitroalkenes due to the polarized double bond which enables them to act as Michael acceptor in conjugate addition reactions, or as a dienophile in cycloaddition makes it an essential synthetic handle for accessing complex molecules. The classical method to prepare nitroolefins is indeed the Henry nitroaldol reaction, where a carbonyl compound and nitroalkane are condensed in presence of base. Direct nitration of olefin, on the other hand, serves as a useful alternative as olefins are abundant, have broad commercial availability and easy to manipulate. In this context, numerous methods have been developed over the last few decades, focusing on direct nitration of styrene and aliphatic olefins. Furthermore, thorough literature search revealed that implementation of this class of reactions are gaining momentum as a preferred pathway to access nitroolefins, despite the presence of a powerful technique such as Henry reaction. In this review, we aim to cover recent advances in direct olefin nitration and their importance in accessing biorelevant molecules, total synthesis targets and future outlook in this specific research area.