Transition metal phosphides (TMP) posses unique physiochemical, geometrical, and electronic properties, which can be exploited for different catalytic applications, such as photocatalysis, electrocatalysis, organic catalysis, etc. Among others, the use of TMP for organic catalysis is less explored and still facing many complex challenges, which necessitate the development of sustainable catalytic reaction protocols demonstrating high selectivity and yield of the desired molecules of high significance. In this regard, the controlled synthesis of TMP‐based catalysts and thorough investigations of underlying reaction mechanisms can provide deeper insights toward practical achievement of desired applications. This review aims at providing a comprehensive analysis on the recent advancements in the synthetic strategies for the tailored and tunable engineering of structural, geometrical, and electronic properties of TMP. In addition, their unprecedented catalytic potential toward different organic transformation reactions is succinctly summarized and critically analyzed. Finally, a rational perspective on future opportunities and challenges in the emerging field of organic catalysis is provided. On the account of the recent achievements accomplished in organic synthesis using TMP, it is highly anticipated that the use of TMP combined with advanced innovative technologies and methodologies can pave the way toward large scale realization of organic catalysis.

Design and development of sustainable metal-free heterogeneous catalysts for organic transformation reactions is a challenging task. In this work, an amine-functionalized graphitic carbon nitride (NH 2 −GCN) was prepared and used as a heterogeneous solid base catalyst for Knoevenagel condensation reaction. The amine functionalization led to increased basicity due to the presence of additional −NH 2 groups. The catalytic potential of NH 2 −GCN was tested for Knoevenagel condensation, which showed good catalytic activity. The detailed optimizations of various reaction conditions, such as time, temperature, solvent, and catalyst amount, were performed. The catalyst showed the highest yield of 92% with excellent selectivity, wherein only a single product was formed. Furthermore, the wide applicability was investigated by studying the substrate scope, and a high turnover number was obtained with almost all the substrates. In addition, green metrics parameters were also determined, and the stability and recyclability of the catalyst were also studied. Overall, the work provides a green, sustainable, and metal-free approach for Knoevenagel condensation reaction.

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One of the important industrial processes commonly employed in the pharmaceutical, explosive, and plastic manufacturing industries is ipso-hydroxylation of arylboronic acids. In this work, a straightforward, metal-free methodology for the synthesis of phenols from arylboronic acids has been demonstrated using hydroxyl functionalized boron nitride (BN−OH) nanosheets. The functionalized hydroxyl groups on the BN nanosheets act as the active sites for the hydroxylation reaction to take place. The detailed optimization of reaction parameters was done in order to attain high catalytic efficiency, and the reactions were conducted in water, which eliminates the use of toxic solvents. The as-synthesized catalysts exhibited excellent recyclability and reusability in addition to high product yields and good turnover numbers. The green metrics parameters were also evaluated for the model reaction to examine the sustainable nature of the developed protocol. The use of BN−OH catalysts for the ipso-hydroxylation reactions under base-free and metal-free conditions using environmentally benign solvents is utmost desired for industrial processes and can pave a way toward sustainable organic catalysis.

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