Copper‐Free One‐Pot Sonogashira‐Type Coupling for the Efficient Preparation of Symmetric Diarylalkyne Ligands for Metal‐Organic Cages**

The often time-consuming and challenging multi-step synthesis of ligands for metal-organic cages is a limiting factor for the discovery and application of new cages. We report a highly efficient copper-free one-pot Sonogashira-type coupling for the preparation of symmetric diarylalkyne ligands on both a small and large scale; bipyridine- and benzimidazole-based ligands for the self-assembly of Co 4 L 6 cages were synthesized in short reaction times and high isolated yields directly from aryl halide precursors. This one-pot method reduces the synthetic burden of ligand synthesis and will facilitate the preparation of ligands with additional functionality for applications of their corre- sponding cages

Copper-Free One-Pot Sonogashira-Type Coupling for the Efficient Preparation of Symmetric Diarylalkyne Ligands for Metal-Organic Cages

Bipyridine- and benzimidazole-based ligands for the self-assembly of Co4L6 cages were synthesised in short reaction times and high isolated yields directly from aryl halide precursors using a copper-free one-pot Sonogashira-type coupling. This one-pot method circumvents the often time-consuming and challenging ligand synthesis for the preparation and application of cages. <br /

The Dynamic Covalent Chemistry of Amidoboronates: Tuning the rac5/rac6 Ratio via the B-N and B-O Dynamic Covalent Bonds

Amidoboronates were prepared as a mixture of up to three isomers (rac5, meso5 and rac6) from the reductive coupling of N-aryl iminoboronates with either cobaltocene or decamethylcobaltocene in acetonitrile. The interconversion of rac5 and rac6 isomers via rearrangement of their dynamic covalent B N bonds was investigated in solution by redissolving isolated crystals. The aniline para substituent and catechol within the amidoboronates tuned the distribution between the rac5 and rac6 isomers; the rac6 isomer predominated for amidoboronates based on pyrocatechol with electron-withdrawing substituents and no interconversion was observed for the rac5 isomers of amidoboronates based on tetrachlorocatechol. Furthermore, the rac5/rac6 distribution was altered by catechol exchange of pyrocatechol for tetrachlorocatechol exploiting the dynamic covalent B O bonds