Automation and microfluidic tools potentially enable efficient, fast, and focused reaction development of complex chemistries, while minimizing resource- and material consumption. The introduction of automation-assisted workflows will contribute to the more sustainable development and scale-up of new and improved catalytic technologies. Herein, the application of automation and microfluidics to the development of a complex asymmetric hydrogenation reaction is described. Screening and optimization experiments were performed using an automated microfluidic platform, which enabled a drastic reduction in the material consumption compared to conventional laboratory practices. A suitable catalytic system was identified from a library of Ru^II-diamino precatalysts. In situ precatalyst activation was studied with ¹H/³¹P nuclear magnetic resonance (NMR), and the reaction was scaled up to multigram quantities in a batch autoclave. These reactions were monitored using an automated liquid-phase sampling system. Ultimately, in less than a week of total experimental time, multigram quantities of the target enantiopure alcohol product were provided by this automation-assisted approach.

Alkoxycarbonylations are important and versatile reactions that result in the formation of a new C-C bond. Herein, we report on a new and halide-free alkoxycarbonylation reaction that does not require the application of an external carbon monoxide atmosphere. Instead, manganese carbonyl complexes and organo(alkoxy)borate salts react to form an ester product containing the target C-C bond. The required organo(alkoxy)borate salts are conveniently generated from the stoichiometric reaction of an organoborane and an alkoxide salt and can be telescoped without purification. The protocol leads to the formation of both aromatic and aliphatic esters and gives complete control over the ester's substitution (e.g., OMe, OtBu, OPh). A reaction mechanism was proposed on the basis of stoichiometric reactivity studies, spectroscopy, and DFT calculations. The new chemistry is particularly relevant for the field of Mn(I) catalysis and clearly points to a potential pathway toward irreversible catalyst deactivation.

Transitioning from fossil fuels to sustainable and green energy sources in mobile applications is a difficult challenge and demands sustained and highly multidisciplinary efforts in R&D. Liquid organic hydrogen carriers (LOHC) offer several advantages over more conventional energy storage solutions, but have not been yet demonstrated at scale. Herein we describe the development of an integrated and compact 25 kW formic acid-to-power system by a team of BSc and MSc students. We highlight a number of key engineering challenges encountered during scale-up of the technology and discuss several aspects commonly overlooked by academic researchers. Conclusively, we provide a critical outlook and suggest a number of developmental areas currently inhibiting further implementation of the technology.

Catalytic reductions of carbonyl-containing compounds are highly important for the safe, sustainable, and economical production of alcohols. Herein, we report on the efficient transfer hydrogenation of ketones catalyzed by a highly potent Mn(I)−NHC complex. Mn−NHC 1 is practical at metal concentrations as low as 75 ppm, thus approaching loadings more conventionally reserved for noble metal based systems. With these low Mn concentrations, catalyst deactivation is found to be highly temperature dependent and becomes especially prominent at increased reaction temperature. Ultimately, understanding of deactivation pathways could help close the activity/stability-gap with Ru and Ir catalysts towards the practical implementation of sustainable earth-abundant Mn-complexes.

The original Fig. 6 presented incorrect thermodynamic data for the conversion 4c + KOtBu → 2 + KOMe. A revised Fig. 6 is now provided. These changes do not affect the article text and its conclusions.

The catalytic asymmetric transfer hydrogenation (ATH) of ketones is a powerful methodology for the practical and efficient installation of chiral centers. Herein, we describe the synthesis, characterization, and catalytic application of a series of manganese complexes bearing simple chiral diamine ligands. We performed an extensive experimental and computational mechanistic study and present the first detailed experimental kinetic study of Mn-catalyzed ATH. We demonstrate that conventional mechanistic approaches toward catalyst optimization fail and how apparently different precatalysts lead to identical intermediates and thus catalytic performance. Ultimately, the Mn-N,N complexes under study enable quantitative ATH of acetophenones to the corresponding chiral alcohols with 75-87% ee.

Catalytic hydrogenation and dehydrogenation reactions form the core of the modern chemical industry. This vast class of reactions is found in any part of chemical synthesis starting from the milligram-scale exploratory organic chemistry to the multi-ton base chemicals production. Noble metal catalysis has long been the key driving force in enabling these transformations with carbonyl substrates and their nitrogen-containing counterparts. This review is aimed at introducing the reader to the remarkable progress made in the last three years in the development of base metal catalysts for hydrogenations and dehydrogenative transformations.

The reaction mechanism of ester hydrogenation catalyzed by a bidentate aminophosphine ligated manganese catalyst was studied by DFT calculations. Particular emphasize was placed on the role of the alkoxide base additives. The presence of such basic promoters as KO^tBu can improve the catalyst activity by lowering the activation barriers of H₂ dissociation as well as the hydrogenation step. The promoting effect of KO^tBu on H₂ activation is much stronger than that of tert-butoxides with other alkali metals, which is crucial for the catalyst regeneration from the deactivated Mn-alkoxide species in the resting state.

Bis-N-heterocyclic carbene (NHC) aminopincer ligands were successfully applied for the first time in the catalytic hydrogenation of esters. We have isolated and characterized a well-defined catalyst precursor as a dimeric [Ru₂(L)₂Cl₃]PF₆ complex and studied its reactivity and catalytic performance. Remarkable initial activities up to 283 000 h^-1 were achieved in the hydrogenation of ethyl hexanoate at only 12.5 ppm Ru loading. A wide range of aliphatic and aromatic esters can be converted with this catalyst to corresponding alcohols in near quantitative yields. The described synthetic protocol makes use of air-stable reagents available in multigram quantities, rendering the bis-NHC ligands an attractive alternative to the conventional phosphine-based systems.

The catalytic reduction of carboxylic acid derivatives has witnessed a rapid development in recent years. These reactions, involving molecular hydrogen as the reducing agent, can be promoted by heterogeneous and homogeneous catalysts. The milestone achievements and recent results by both approaches are discussed in this Review. In particular, we focus on the mechanistic aspects of the catalytic hydrogenation and highlight the bifunctional nature of the mechanism that is preferred for supported metal catalysts as well as homogeneous transition metal complexes.

The use of hydrogen as a fuel requires both safe and robust technologies for its storage and transportation. Formic acid (FA) produced by the catalytic hydrogenation of CO₂ is recognized as a potential intermediate H ₂ carrier. Herein, we present the development of a formate-based H₂ storage system that employs a Ru PNP-pincer catalyst. The high stability of this system allows cyclic operation with an exceptionally fast loading and liberation of H₂. Kinetic studies highlight the crucial role of the base promoter, which controls the rate-determining step in FA dehydrogenation and defines the total H₂ capacity attainable from the hydrogenation of CO₂. The reported findings show promise for the development of practical technologies that use formic acid as a hydrogen carrier. Like pinning down an ant: An Ru PNP catalyst provides unprecedented rates of CO₂ hydrogenation up to 1 100 000 h^-1 (turnover number >200 000) and excellent activity in the dehydrogenation of formic acid in DMF if used with the non-nucleophilic 1,8-diazabicyclo[5.4.0]undec-7-ene base. Unlike amine-based systems, this medium allows us to achieve high formate capacity together with rapid H₂ charging and release.