A C-to-O atom-swapping reaction sequence enabled by Ni-catalyzed decarbonylation of lactones

Abstract

Advances in site-selective functionalization reactions have enabled single atom changes on the periphery of a complex molecule, but reaction manifolds that enable such changes on the core framework of the molecule remain sparse. Here, we disclose a strategy for carbon-to-oxygen substitution in cyclic diarylmethanes and diarylketones to yield cyclic diarylethers. Oxygen atom insertion is accomplished by methylene and Baeyer–Villiger oxidations. To remove the carbon atom in this C-to-O “atom swap” process, we developed a nickel-catalyzed decarbonylation of lactones to yield the corresponding cyclic diaryl ethers. This reaction was enabled by mechanistic studies with stoichiometric nickel(II) complexes that led to the optimization of a ligand capable of promoting a challenging C(sp²)–O(aryl) reductive elimination. The nickel-catalyzed decarbonylation was applied to 6–8 membered lactones (16 examples, 32–99%). Finally, a C-to-O atom-swapping reaction sequence was accomplished on a natural product and a pharmaceutical precursor.