@article { , title = {Umpolung Synthesis of Pyridyl Ethers by Bi(V)‐Mediated O‑Arylation of Pyridones}, abstract = {We report that O-selective arylation of 2- and 4-pyridones with arylboronic acids is affected by a modular, bismacycle-based system. The utility of this umpolung approach to pyridyl ethers, which is complementary to conventional methods based on S N Ar or cross-coupling, is demonstrated through the concise synthesis of Ki6783 and picolinafen, and the formal synthesis of cabozantib and golvatinib. Computational investigations reveal that arylation proceeds in a concerted fashion via a 5-membered transition state. The kinetically-controlled regioselectivity for O-arylation – which is reversed relative to previous Bi(V)-mediated pyridone arylations – is attributed primarily to the geometric constraints imposed by the bismacyclic scaffold.}, doi = {10.1002/anie.202212873}, eissn = {1521-3773}, issn = {1433-7851}, issue = {51}, journal = {Angewandte Chemie - International Edition}, publicationstatus = {Published}, publisher = {Wiley}, url = {https://nottingham-repository.worktribe.com/output/12898568}, volume = {61}, year = {2022}, author = {Ruffell, Katie and Gallegos, Liliana and Ling, Kenneth and Paton, Robert S. and Ball, Liam T.} }