Homogeneous catalysis has provided chemists with numerous transformations to enable rapid construction of organic molecules. However, these reactions are complex, requiring multiple substrate‐dependent mechanistic steps to operate in harmony under a single set of experimental conditions. As a consequence, synthetic chemists often carry out laborious, empirical screening to identify suitable catalysts, solvents, and additives to achieve high yields and selectivity. In this Minireview, recently developed tools, technologies, and strategies will be described that improve this development process. In particular, the application of high throughput techniques to run more experiments, experimental design principles to access better data, and statistical tools to provide predictive models will be discussed.

An intermolecular coupling of primary alcohols and organotriflates has been developed to provide ketones by the action of a Ni(0) catalyst. This oxidative transformation is proposed to occur by the union of three distinct catalytic cycles. Two competitive oxidation processes generate aldehyde in situ via hydrogen transfer oxidation or (pseudo)­dehalogenation pathways. As aldehyde forms, a Ni-catalyzed carbonyl-Heck process enables formation of the key carbon–carbon bond. The utility of this rare alcohol to ketone transformation is demonstrated through the synthesis of diverse complex and bioactive molecules.

We report a catalytic method to access secondary alcohols by the coupling of aryl iodides. Either aldehydes or alcohols can be used as reaction partners, making the transformation reductive or redox-neutral, respectively. The reaction is mediated by a Ni catalyst and a 1,5-diaza-3,7-diphospha­cyclooctane. This P2N2 ligand, which has previously been unrecognized in cross-coupling and related reactions, was found to avoid deleterious aryl halide reduction pathways that dominate with more traditional phosphines and NHCs. An interrupted carbonyl-Heck type mechanism is proposed to be operative, with a key 1,2-insertion step forging the new C–C bond and forming a nickel alkoxide that may be turned over by an alcohol reductant. The same catalyst was also found to enable synthesis of ketone products from either aldehydes or alcohols, demonstrating control over the oxidation state of both the starting materials and products.

A procedure is presented that enables the direct deuteration of the formyl C–H bond of aldehydes using D2O as the deuterium source and commercially available RuHCl(CO)(PPh3)3 as the catalyst. Up to 84% deuterium incorporation can be achieved in a single experiment. Multiple iterations can be carried out to further increase the deuteration.

Die homogene Katalyse stellt Chemikern zahlreiche Transformationen zur Verfügung, die einen raschen Aufbau organischer Moleküle ermöglichen. Allerdings sind diese Reaktionen komplex, da sie viele substratabhängige mechanistische Schritte erfordern, die harmonisch unter einheitlichen experimentellen Bedingungen ablaufen müssen. Infolgedessen führen Synthesechemiker oftmals arbeitsintensive empirische Studien durch, um geeignete Katalysatoren, Lösungsmittel und Additive zu ermitteln, mit denen hohe Ausbeuten und Selektivitäten erreicht werden können. In diesem Kurzaufsatz werden neu entwickelte Hilfsmittel, Techniken und Strategien beschrieben, die diesen Entwicklungsprozess verbessern. Speziell die Anwendung von Hochdurchsatzverfahren zur Durchführung von mehr Experimenten, Prinzipien der Versuchsplanung und statistische Hilfsmittel für Vorhersagemodelle werden diskutiert.