Alkyne metathesis is increasingly explored as a reliable method to close macrocyclic rings, but there are no prior examples of an alkyne-metathesis-based homodimerization approach to natural products. In this approach to the cytotoxic C2-symmetric marine-derived bis(lactone) disorazole C1, a highly convergent, modular strategy is employed featuring cyclization through an ambitious one-pot alkyne cross-metathesis/ring-closing metathesis self-assembly process.

Microorganisms can be programmed to perform chemical synthesis via metabolic engineering.However,despite an increasing interest in the use of de novo metabolic pathways and designer whole-cells for small molecule synthesis,t he inherent synthetic capabilities of native microorganisms remain underexplored. Herein, we report the use of unmodified E. coli BL21(DE3) cells for the reduction of keto-acrylic compounds and apply this whole-cell biotransformation to the synthesis of aminolevulinic acid from al ignin-derived feedstock.T he reduction reaction is rapid, chemo-, and enantioselective,occurs under mild conditions (37 8 8C, aqueous media), and requires no toxic transition metals or external reductants. This study demonstrates the remarkable promiscuity of central metabolism in bacterial cells and how these processes can be leveraged for synthetic chemistry without the need for genetic manipulation.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

Phosphorus heterocycles have been extensively studied over the past 100 years, yet for many chemists some of the most useful synthetic routes to these cycles remain unknown. These phosphorus‐containing compounds have long been seen as the “holy grail” for the chemical industries, promising not only better physical‐chemical properties and novelty in terms of intellectual property, but also for academic researchers intrigued by their challenging accessibility. Every chemist who has worked with phosphorus derivatives knows that this heteroatom is always a great source of surprises and can often lead to ground‐breaking findings. This review aims to guide readers through the various synthetic routes for the formation of monocyclic pentavalent phosphorus heterocycles of key importance in the development of future new and original chemical entities.

Chloromethyl triazoles are shown to be cysteine selective alkylation reagents for ‘near-native’ post-translational modification of protein and peptide substrates.

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