Angewandte Chemie International Edition

León, Iker; Alonso, Elena R.; Mata, Santiago; Cabezas, Carlos; Alonso, Jose Luis

doi: 10.1002/anie.201984561pmid: N/A

Picheau, Emmanuel; Hof, Ferdinand; Derré, Alain; Daffos, Barbara; Pénicaud, Alain

doi: 10.1002/anie.201912696pmid: N/A

Yang, Meijia; Zhang, You; Jian, Junhua; Fang, Long; Li, Jing; Fang, Zhengsong; Yuan, Zhongke; Dai, Liming; Chen, Xudong; Yu, Dingshan

doi: 10.1002/anie.201912599pmid: N/A

doi: 10.1002/anie.201984511pmid: N/A

Wu, Xiaojian; Kim, Mijin; Kwon, Hyejin; Wang, YuHuang

doi: 10.1002/anie.201911757pmid: 31651096

doi: 10.1002/anie.201905777pmid: N/A

Dickschat, Jeroen S.

doi: 10.1002/anie.201905312pmid: 31183935

This Minireview summarises recent developments in the biosynthesis of diterpenes by diterpene synthases in bacteria. It is structured by the class of enzyme involved in the first committed step towards diterpenes, starting with type I diterpene synthases, followed by type II enzymes and the more recently discovered UbiA‐related diterpene synthases. A special emphasis lies on the reaction mechanisms of diterpene synthases that convert simple linear precursors through cationic cascades into structurally complex, usually polycyclic carbon skeletons with multiple stereogenic centres. A further main focus of this Minireview is a discussion of how these mechanisms can be unravelled. Downstream modifications to bioactive molecules are also covered.

Aspern, N.; Röschenthaler, G.‐V.; Winter, M.; Cekic‐Laskovic, I.

doi: 10.1002/anie.201901381pmid: 31339214

Further enhancement in the energy densities of rechargeable lithium batteries calls for novel cell chemistry with advanced electrode materials that are compatible with suitable electrolytes without compromising the overall performance and safety, especially when considering high‐voltage applications. Significant advancements in cell chemistry based on traditional organic carbonate‐based electrolytes may be successfully achieved by introducing fluorine into the salt, solvent/cosolvent, or functional additive structure. The combination of the benefits from different constituents enables optimization of the electrolyte and battery chemistry toward specific, targeted applications. This Review aims to highlight key research activities and technical developments of fluorine‐based materials for aprotic non‐aqueous solvent‐based electrolytes and their components along with the related ongoing scientific challenges and limitations. Ionic liquid‐based electrolytes containing fluorine will not be considered in this Review.

León, Iker; Alonso, Elena R.; Mata, Santiago; Cabezas, Carlos; Alonso, Jose Luis

doi: 10.1002/anie.201907222pmid: 31448858

Neutral glutamine has been evaporated by laser ablation of its solid sample to seed a rare gas carrier prior to a supersonic expansion and proved by Fourier transform microwave techniques. We report on three distinct neutral conformers that show a singular non‐interacting and flexible amide sidechain in contrast with the other proteinogenic aliphatic amino acids. It could explain the essential biological role of glutamine as a nitrogen source, and its unique ability to form a variety of hydrogen bonds with peptide backbones. Common computational methods fail to predict the delicate balance of intramolecular interactions controlling the geometry of the most stable conformer. The spectroscopic data here reported can be used to benchmark novel computational methods in quantum chemistry.

Zang, Yaping; Stone, Ilana; Inkpen, Michael S.; Ng, Fay; Lambert, Tristan H.; Nuckolls, Colin; Steigerwald, Michael L.; Roy, Xavier; Venkataraman, Latha

doi: 10.1002/anie.201906215pmid: 31226235

A single‐molecule method has been developed based on the scanning tunneling microscope (STM) to selectively couple a series of aniline derivatives and create azobenzenes. The Au‐catalyzed oxidative coupling is driven by the local electrochemical potential at the nanostructured Au STM tip. The products are detected in situ by measuring the conductance and molecular junction elongation and compared with analogous measurements of the expected azobenzene derivatives prepared ex situ. This single‐molecule approach is robust, and it can quickly and reproducibly create reactions for a variety of anilines. We further demonstrate the selective synthesis of geometric isomers and the assembly of complex molecular architectures by sequential coupling of complementary anilines, demonstrating unprecedented control over bond formation at the nanoscale.