Robby Vroemans

Abstract

Substituted 4-acetyl-3-hydroxy-3-pyrroline-2-ones have been prepared via three-component reactions and the tautomerism of these 3-pyrroline-2-ones is due to the slight difference of energy, and the significantly large rate constant of transformation between two tautomers. 1,4,5-Trisubstituted pyrrolidine-2,3-dione derivatives were prepared from the above mentioned 2-pyrrolidinone derivatives and aliphatic amines, which exist in enamine form and are stabilized by an intramolecular hydrogen bond. A possible reaction mechanism between 3-pyrroline-2-one and aliphatic amine (CH₃NH₂) was proposed based on computational results and the main product is formed favorably following the PES via the lowest ΔG^# pathway in both the gas-phase and an ethanol solvent model. DFT calculations showed that kinetic selectivity is more significant than thermodynamic selectivity for forming main products.

Beilstein J. Org. Chem. 2022, 18, 1140–1153. doi:10.3762/bjoc.18.118

Nature Communications, Published online: 29 August 2022; doi:10.1038/s41467-022-32850-8

Nature Chemistry, Published online: 26 August 2022; doi:10.1038/s41557-022-01031-x

R. B. Woodward received his early education in MO theory from the theoretical chemist William E. Moffitt (left) and needed to apply it to explain his 5th mysterious reaction in the course of his failed route to vitamin B₁₂. This paper discusses “Why it was Woodward” who, together with Roald Hoffmann, solved the pericyclic no-mechanism problem.

Abstract

This publication discusses R. B. Woodward's motivations, personality qualities, and chemical experiences that placed him in a perfect position to discover, along with Roald Hoffmann, the solution to the pericyclic no-mechanism problem, that is, to discover the Woodward-Hoffmann rules or, as Woodward preferred, the Principle of Conservation of Orbital Symmetry.

Publication date: Available online 25 August 2022

Source: Chem

Author(s): Leila Zamani, Patricia Z. Musacchio

Publication date: 28 September 2022

Source: Tetrahedron Letters, Volume 107

Author(s): Dejin Zhang, Shu Sun, Zehua Qian, Kangle Pei, Xueyu Shang, Chengcheng Liu, Pan Guo

Publication date: 8 October 2022

Source: Tetrahedron, Volume 124

Author(s): Yuanyuan Lu, Huining Chai, Kun Yu, Chaonan Huang, Yujie Li, Jinyu Wang, Jiping Ma, Weiqiang Tan, Guangyao Zhang

Nature Synthesis, Published online: 18 August 2022; doi:10.1038/s44160-022-00138-w

To catalyse or not to catalyse, that is the question. Whether it is nobler to have a catalyst that speeds up a reaction or it is cheaper for the reaction to proceed on its own. The reaction between aldehydes and malononitrile raises a Hamletic doubt: is there a need for a catalyst?

Abstract

The aim of this Perspective is to start a discussion about the real usefulness of more or less sophisticated catalytic systems for the Knoevenagel reaction with malononitrile, a reaction that can take place under mild conditions without the need of a catalyst. From a sustainable viewpoint the questions are: Is it useful to increase the rate of a reaction that already occurs under mild conditions? Is it useful to spend resources and time in designing, characterizing and realizing complex catalytic systems for such reaction? Does it make sense to carry out the reaction under conditions such as to have a slower reaction rate and therefore to find a catalyst that is able to increase it?

This Viewpoint Article provides tips on how to increase the chances of securing a European Research Council (ERC) Starting Grant.

Abstract

European Research Council (ERC) Starting Grants are arguably the most competitive grants in Europe and their prestige is fully justified considering that they (i) allow focus on a high risk/high gain project through generous funding of 1.5–2 million Euros, (ii) they can enable the foundation of a new academic group and earn the submitting principal investigator a professorship, and (iii) they serve as a highly reputable award that can either facilitate tenure/promotion or assist in securing a subsequent academic position. However, the journey to getting one is far from easy. In this Viewpoint Article, I will discuss my first two unsuccessful attempts to secure an ERC Starting Grant and how the lessons learned during the process led me to ultimately secure a grant upon my third attempt.

The progresses achieved in the synthesis of polyureas and polyurea hybrids directly or indirectly from CO₂ have been reviewed, including the method, monomer structure, catalyst and properties.

Abstract

The utilization of CO₂ as a renewable and cheap carbon resource to produce fuels, chemicals and polymers has attracted more attention. This review will summarize the developments in the production of polymers like polyureas and polyurea hybrids with CO₂ as a monomer directly or indirectly. The influences of catalyst and the structure of diamine monomer on the molecular weight, thermal stability and mechanical properties of polyureas are discussed. In addition, the general properties and applications of functional CO₂-based polyureas are also described. A few examples of CO₂-based polyurea hybrids are also introduced. Finally, the future research priorities as well as the development trend of polyurea materials are depicted.

A simple and green visible-light-initiated strategy has been developed for the installation of cyano and azido groups through multi-component reaction of α-diazoesters, cyclic ethers and TMSCN/TMSN₃. A number of structurally diverse organic nitriles and azides could be efficiently obtained in moderate to good yields with favorable functional group tolerance at room temperature.

Abstract

A simple and green visible-light-initiated strategy for the installation of cyano and azido groups has been established through multi-component reaction of α-diazoesters, cyclic ethers and TMSCN/TMSN₃. A number of structurally diverse organic nitriles and azides could be efficiently obtained at room temperature without adding any external metal reagent, strong oxidant, base and photocatalyst. The synthetic transformations of the reaction products to some functionalized molecules were carried out to highlight the potential utility of this method.

Synthesis
DOI: 10.1055/a-1894-8826

We demonstrate an iridium-catalyzed alkylation of ketones with alcohols, which enables one-step access to donepezil, cyclic ketones, and linear ketones in high yields. A scale-up experiment shows the excellent practicability of this protocol. Comparative experiments show that a small amount of water is beneficial to the improvement of product yield.
[...]

Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany

Article in Thieme eJournals:
Table of contents  |  Abstract  |  Full text

Nature Synthesis, Published online: 15 August 2022; doi:10.1038/s44160-022-00156-8

The Cover Feature shows an illustration of a Rubik's Cube symbolizing the molecular isomerization of methyl formate to acetic acid. The seemingly simple rearrangement occurs via a complex catalytic manifold comprising NaOMe for the decarbonylation of HCO₂CH₃, NaI for the activation of methanol, and a molecular Pd-complex for the recombination of the components. This isomerization of methyl formate, which in turn can be produced from CO₂ and green H₂, offers a a “Power-to-X” route to acetic acid. More information can be found in the Research Article by P. Jürling-Will et al.

Nature, Published online: 11 August 2022; doi:10.1038/d41586-022-02161-5