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Macrocyclic peptides containing C(sp2)–C(sp3) side chain cross-links are a rapidly growing subclass of ribosomally synthesized and post-translationally modified peptides (RiPPs), with significant potential in the development of new pharmaceuticals. This report presents a method for the efficient synthesis of derivatives of this class using a diastereoselective cross-electrophile coupling for the formation of the key β-aryl-alkyl cross-link. 

We investigate the electronic shot noise produced by nanowires of β-Ta, an archetypal “bad” metal with resistivity near the Ioffe–Regel localization limit. The Fano factor characterizing the shot noise exhibits a strong dependence on temperature and is suppressed compared to the expectations for quasiparticle diffusion, but hopping transport is ruled out by the analysis of scaling with the nanowire length. These anomalous behaviors closely resemble those of strange metal nanowires, suggesting that β-Ta may host a correlated electron liquid. This material provides an accessible platform for exploring exotic electronic states of matter. 

Nitrogen‐containing compounds are valuable synthetic intermediates and targets in nearly every chemical industry. While methods for nitrogen‐carbon and nitrogen‐heteroatom bond formation have primarily relied on nucleophilic nitrogen atom reactivity, molecules containing nitrogen‐halogen bonds allow for electrophilic or radical reactivity modes at the nitrogen center. Despite the growing synthetic utility of nitrogen‐halogen bond‐containing compounds, selective catalytic strategies for their synthesis are largely underexplored. We recently discovered that the vanadium‐dependent haloperoxidase (VHPO) class of enzymes are a suitable biocatalyst platform for nitrogen‐halogen bond formation. Herein, we show that VHPOs perform selective halogenation of a range of substituted benzamidine hydrochlorides to produce the corresponding N’‐halobenzimidamides. This biocatalytic platform is applied to the synthesis of 1,2,4‐oxadiazoles from the corresponding N‐acylbenzamidines in high yield and with excellent chemoselectivity. Finally, the synthetic applicability of this biotechnology is demonstrated in an extension to nitrogen‐nitrogen bond formation and the chemoenzymatic synthesis of the Duchenne muscular dystrophy drug, ataluren. 

Structural distortion of the secondary coordination sphere driven by the incorporation of an alkali metal in Ce³⁺imidophosphorane complexes tunes the Ce^3+/4+oxidation potential.