Catalytic acceptorless dehydrogenative borylation of styrenes enabled by a molecularly defined manganese complex.

In this study, we employed a 3d metal complex as a catalyst to synthesize alkenyl boronate esters through the dehydrogenative coupling of styrenes and pinacolborane. The process generates hydrogen gas as the sole byproduct without requiring an acceptor, rendering it environmentally friendly and atom-efficient. This methodology demonstrated exceptional selectivity for dehydrogenative borylation over direct hydroboration. Additionally, it exhibited a preference for borylating aromatic alkenes over aliphatic ones. Notably, derivatives of natural products and bioactive molecules successfully underwent diversification using this approach. The alkenyl boronate esters served as precursors for the synthesis of various pharmaceuticals and potential anticancer agents. Our research involved comprehensive experimental and computational studies to elucidate the reaction pathway, highlighting the B-H bond cleavage as the rate-determining step. The catalyst's success was attributed to the hemilability and metal-ligand bifunctionality of the ligand backbone.

Variable structure diversification by multicatalysis: the case of alcohols.

Given that alcohol moieties are present in a great diversity of valuable fine chemicals from nature and synthesis, methods enabling their structure diversification are highly sought after. Catalysis proved to enable the development of new transformations that are beyond the inherent reactivity of alcohols. However, modifying the structure of alcohols at certain unbiased positions remains a major challenge or requires tedious multistep procedures. Recently, increased attention has been given to multicatalyis, which combines multiple reactions and catalysts within one system, creating room for discovering previously inaccessible reactivities or increasing the overall efficiency of multistep transformations. This feature article focuses on demonstrating various aspects of devising such multicatalytic systems that modify the structure of alcohol-containing compounds. Special attention is given to highlighting the challenges and advantages of multicatalysis, and in a broader context discussing how the field of catalysis may progress toward more complex systems.

Manganese-catalyzed hydrogenation, dehydrogenation, and hydroelementation reactions.

The emerging field of organometallic catalysis has shifted towards research on Earth-abundant transition metals due to their ready availability, economic advantage, and novel properties. In this case, manganese, the third most abundant transition-metal in the Earth's crust, has emerged as one of the leading competitors. Accordingly, a large number of molecularly-defined Mn-complexes has been synthesized and employed for hydrogenation, dehydrogenation, and hydroelementation reactions. In this regard, catalyst design is based on three pillars, namely, metal-ligand bifunctionality, ligand hemilability, and redox activity. Indeed, the developed catalysts not only differ in the number of chelating atoms they possess but also their working principles, thereby leading to different turnover numbers for product molecules. Hence, the critical assessment of molecularly defined manganese catalysts in terms of chelating atoms, reaction conditions, mechanistic pathway, and product turnover number is significant. Herein, we analyze manganese complexes for their catalytic activity, versatility to allow multiple transformations and their routes to convert substrates to target molecules. This article will also be helpful to get significant insight into ligand design, thereby aiding catalysis design.

Advancements in multifunctional manganese complexes for catalytic hydrogen transfer reactions.

Catalytic hydrogen transfer reactions have enormous academic and industrial applications for the production of diverse molecular scaffolds. Over the past few decades, precious late transition-metal catalysts were employed for these reactions. The early transition metals have recently gained much attention due to their lower cost, less toxicity, and overall sustainability. In this regard, manganese, which is the third most abundant transition metal in the Earth's crust, has emerged as a viable alternative. However, the key to the success of such manganese-based complexes lies in the multifunctional ligand design and choice of appropriate ancillary ligands, which helps them mimic and, even in some cases, supersede noble metals' activities. The metal-ligand bifunctionality, achieved via deprotonation of the acidic C-H or N-H bonds, is one of the powerful strategies employed for this purpose. Alongside, the ligand hemilability in which a weakly chelating group tunes in between the coordinated and uncoordinated stages could effectively stabilize the reactive intermediates, thereby facilitating substrate activation and catalysis. Redox non-innocent ligands acting as an electron sink, thereby helping the metal center in steps gaining or losing electrons, and non-classical metal-ligand cooperativity has also played a significant role in the ligand design for manganese catalysis. The strategies were not only employed for the chemoselective hydrogenation of different reducible functionalities but also for the C-X (X = C/N) coupling reactions via HT and downstream cascade processes. This article features multifunctional ligand-based manganese complexes, highlighting the importance of ligand design and choice of ancillary ligands for achieving the desired catalytic activity and selectivity for HT reactions. We have also discussed the detailed reaction pathways for metal complexes involving bifunctionality, hemilability, redox activity, and indirect metal-ligand cooperativity. The synthetic utilization of those complexes in different organic transformations has also been detailed.

Selective Hydroboration of Carboxylic Acids with a Homogeneous Manganese Catalyst.

Catalytic reduction of carboxylic acid to the corresponding alcohol is a challenging task of great importance for the production of a variety of value-added chemicals. Herein, a manganese-catalyzed chemoselective hydroboration of carboxylic acids has been developed with a high turnover number (>99 000) and turnover frequency (>2000 h-1) at 25 °C. This method displayed tolerance of electronically and sterically differentiated substrates with high chemoselectivity. Importantly, aliphatic long-chain fatty acids, including biomass-derived compounds, can efficiently be reduced. Mechanistic studies revealed that the reaction occurs through the formation of active manganese-hydride species via an insertion and bond metathesis type mechanism.