Rhodium-Catalyzed Chemo-Divergent Reaction between Oxetan-3-ones/Azetidin-3-ones and Arylboronic Acids.

Herein, we report a rhodium-catalyzed chemo-divergent reaction of oxetan-3-one and azetidin-3-ones with arylboronic acids. Ligand and temperature control selectively provide access to either tertiary alcohols (3-aryl oxetanols/azetidinols) via direct carbonyl addition or α-oxy/α-amino ketones via β-carbon elimination-initiated ring opening. This methodology bypasses stoichiometric organometallic reagents and specialized precursors, offering broad functional group tolerance and efficient access to carboxylic acid bioisosteres, while establishing a versatile catalytic platform for diversifying aliphatic small-ring systems in drug discovery.