No abstract

5-Oxazoyl-sulfamates have been profiled as versatile building blocks for modifications of oxazoles with various nucleophiles. The unified approach provides a diversification platform to directly access 5-amino-oxazoles, 5-oxazolyl-sulfides, and 5-oxazoyl-aryl ethers from a single precursor.

Methanobactin OB3b (Mbn-OB3b) is a unique natural product featuring two ene-thiolate-azlactone rings incorporated in a rigidified peptide backbone. The stunning affinity of this chalkophore for copper (Ka ≈ Cu(I) 10E34) makes it a prominent lead compound for Cu-transport, metabolism, and detoxification. Its exceptional structure poses particular challenges for biosynthesis and chemical manipulation. Here, we report the first total synthesis of Cu(I)-bounded methanobactin OB3b featuring as key transformations a cyclodehydration-thioacylation sequence, to generate the conjugated heterocyclic systems, and a copper-templated cyclization, to complete the caged structure of the sensitive chalkophore.

Methanobactin OB3b (Mbn‐OB3b) is a unique natural product with stunning affinity for copper ions (Ka ≈ Cu(I) 1034). Here, we report the first total synthesis of Cu(I)‐bound methanobactin OB3b featuring as key transformations a cyclodehydration‐thioacylation sequence, to generate the conjugated heterocyclic systems, and a copper‐templated cyclization, to complete the caged structure of the very sensitive target compound.