Aminoazanium of DABCO: An Amination Reagent for Alkyl and Aryl Pinacol Boronates

Abstract The aminoazanium of DABCO (H 2 N‐DABCO) has been developed as a general and practical amination reagent for the direct amination of alkyl and aryl pinacol boronates. This compound is stable and practical for use as a reagent. Various primary, secondary. and tertiary alkyl−Bpin and aryl−Bpin substrates were aminated to give the corresponding amine derivatives. The amination is stereospecific. The anti‐Markovnikov hydroamination of olefins was easily achieved by catalytic hydroboration with HBpin and in subsequent situ amination using H 2 N‐DABCO. Moreover, the combination of 1,2‐diboration of olefins, using B 2 pin 2 , with this amination process achieved the unprecedented 1,2‐diamination of olefins. The amination protocol was also successfully extended to aryl pinacol boronates.