Dehomologative C-C Borylation of Aldehydes and Alcohols via a Rh-Catalyzed Dehydroformylation-Borylation Relay.

The dehomologative conversion of linear or α-methyl aldehydes to vinyl boronates is achieved via a one-pot sequence of rhodium-catalyzed transfer dehydroformylation and transfer borylation of the resulting alkenes. Similarly, allylic or aliphatic alcohols are converted to vinyl boronates through a sequence involving, respectively, rhodium-catalyzed isomerization or transfer dehydrogenation to aldehyde intermediates, followed by dehydroformylation-borylation. The vinyl boronates can be further hydrogenated to alkyl boronates using the same rhodium precatalyst, enabling all five catalytic steps with a single catalyst system.