Marnix van der Kolk

We herein present a bench-stable fluorophosphine-based nickel(0) complex [Ni(PFPh2)4] (1), which is highly stable in air and water. This complex does not only incorporate a nickel centre in the zero-oxidation state, but also includes fluorophosphine ligands. Since these ligands typically tend to disproportionation in solution, they represent a vastly underexplored ligand class. [Ni(PFPh2)4] can be obtained from a one-pot reaction of [Ni(MeCN)4](BF4)2 with Ph2P(=O)–PPh2, involving a unique in-situ reduction of Ni(II) to Ni(0) and the simultaneous fluorination by the BF4– anion. The application of [Ni(PFPh2)4] as highly stable Ni(0) pre-catalyst in combination with additional phosphine ligands, such as dppf (1,1'-bis(diphenylphosphino)ferrocene) in Suzuki-Miyaura coupling reactions uncovers its high catalytic activity, which is greatly superior to the conventional Ni(0) source [Ni(COD)2]. A remarkable catalytic activity is achieved through the combination of 1 and dppf after a light-induced activation of the complex.

Nature, Published online: 30 August 2024; doi:10.1038/d41586-024-02861-0

Ever-enlarging vehicles take more energy to build and run. Plus, the biggest-ever catalogue of food microbes and how pregnancy transforms the brain.

Advanced Synthesis &Catalysis, Volume 366, Issue 16, Page 3404-3404, August 20, 2024.

Nature, Published online: 28 August 2024; doi:10.1038/d41586-024-02737-3

Insects are thought to use specific chest muscles to actively open and close their wings. However, high-speed imaging reveals that rhinoceros beetles flap their hindwings to deploy them for flight, and use their forewings to push their hindwings back to rest. This inspired the design of flapping microrobots with self-deploying, self-retracting wings.

Nature Synthesis, Published online: 28 August 2024; doi:10.1038/s44160-024-00621-6

Integrating electrochemical CO electrolysers with a bioreactor can yield high-value long-chain carbon products, but the electrolytes for the two systems are mismatched. Now, a porous solid electrolyte reactor, which can produce acetate directly in bioelectrolyte, is demonstrated. Direct integration with a bioreactor produces bioplastic from CO via the acetate intermediate.

Cyano groups represent an important class of functional motifs in medicinal chemistry given their synthetic versatility and capacity to engage in essential interactions with biological targets. However, the synthesis of sterically hindered alkyl nitriles using non-toxic reagents remains challenging. Traditional methods often rely on toxic cyanide sources and suffer from limited substrate scope. Herein, we report a photoredox catalyzed, metal-free deoxycyanation of alkyl alcohols that allows rapid access to a wide array of 1º, 2º, and 3º cyanides using non-toxic cyanide reagents.

Gold, in contrast to other transition metals, offers a unique reactivity profile and has emerged as an efficient tool in the field of synthetic organic chemistry. This review will focus on recent advances in gold-catalyzed Heck and Suzuki-type reactions, particularly those facilitated by photocatalysts and ligand design.

Abstract

Transition metal-catalyzed Suzuki and Heck reactions are two of the most common carbon-carbon bond formation reactions. Gold, unlike other transition metals (Pd, Ni, and Cu), offers unique reactivity profiles, and has emerged as an efficient tool in the field of synthetic organic chemistry. This mini-review focused on the recent work in gold-catalyzed Heck and Suzuki-type reactions, especially by photocatalysts or ligand design, which show reactivities and features distinct from other transition metals. These discoveries will further facilitate the development of gold redox catalysis as well as applications in organic synthesis, biochemistry, and medicinal chemistry.

Carbon dots are cheap and environmentally friendly nanomaterials that appear as promising components of artificial photosynthetic systems. However, their photo-catalytic properties have rarely been studied in such detail that would enable a judicious design based on structure-activity relationships. Key are molecular species included in the carbon dot structure and the kinetic competition between different processes that might take place upon photo-excitation. Significant progress is expected from intertwined precursor choice, purification procedures, spectroscopic characterization, and theoretical calculations.

Abstract

We have developed a Ni-catalyzed cyclodimerization of 1,6-allenyenes which affords pentacyclic derivatives containing a [3]-ladderane. Six new carbon-carbon bonds are formed in a single operation which is fully atom-economical. The reaction proceeds with an inexpensive catalyst and shows a broad scope in the alkyne, the allene and the tethering group. A computational and experimental study on the reaction mechanism suggests that this process proceeds by oxidative cyclometallation of the allenyne coordinated to Ni(0) followed by reductive elimination leading to cyclobutenes. Then, two of these molecules are coupled following a related cyclometallation-reductive elimination sequence, the latter being the rate-limiting step.

The front cover picture shows two of the founders of fluorine chemistry, Carl Wilhelm Scheele and Henri Moissan, and examples of the fluorine-containing compounds reported in the articles that appear in this special issue of Advanced Synthesis & Catalysis. More information about this issue can be found in the Commentary by the Issue Editor, Véronique Gouverneur (V. Gouverneur, Adv. Synth. Catal. 2024, 366, 3404–3404; DOI: 10.1002/adsc.202400881)

Motorized transport is not only unsustainable, but also causes several negative effects in cities. In this paper, we investigated whether a substantial increase in fuel prices could lead to more people switching to bicycle sharing systems.

Electro-organic synthesis, evolved as a sustainable and scalable approach in fluoriation chemistry, received rapid development recently. As a result, many novel and attracting applications of introduction of fluorine atoms into organic compounds by direct and redox-mediated electrochemical methods has been reported, especially in recent five years. In this review, the reaction scopes, reaction mechanism, the fundamental aspects and the fluorine source variation in electrochemcial fluoriation transformation are highlighted.

Abstract

Ideal pathways to synthesize fluorinated compounds were pursued for over 100 years, due to wide application of organofluorides in materials, agrochemicals and pharmaceuticals. In this regard, electro-organic synthesis, evolved as a sustainable and scalable approach in various synthetic protocols, stands out as a promising strategy. As a result, many novel and attracting applications of introduction of fluorine items into organic compounds by direct and redox-mediated electrochemical methods has been reported, especially in recent five years. In this review, we are aim to highlight the reaction scopes, reaction mechanism, the fundamental aspects and the fluorine source variation in electrochemcial fluoriation transformation.