Access to Cyclic Amino Boronates via Rhodium-Catalyzed Functionalization of Alkyl MIDA Boronates

Herein, we describe the rhodium-catalyzed C–H amination reaction of 1,2-boryl sulfamate esters derived from amphoteric α-boryl aldehydes. Depending on the substitution pattern of the boryl sulfamate ester, a diverse range of five- or six-membered ring heterocycles are accessible using this transformation. The highly chemoselective nature of the C–H functionalization reaction preserves the alkyl boronate functional group, which enables the synthesis of B–C–N and B–C–C–N motifs that are present in a number of hydrolase inhibitors.