Palladium-Catalyzed Diamination of Olefins

Abstract

Complementary to previous approaches to diaminate olefins and as an extension to the group’s previous work in the area (H. Du, B. Zhao, Y. Shi J. Am. Chem. Soc. 2007, 129, 762), terminal olefins were diaminated at allylic and homoallylic carbons by a Pd-catalyzed C-H insertion under solvent-free conditions. The nitrogen source is di-tert-butyldiaziridinone, which can be synthesized in a few steps. The scope encompasses both monosubstituted and 1,1-disubstituted terminal olefins, and the resulting products can be converted into the free diamine by treatment with TFA and concentrated acid. Diamination is also possible, with 1,9-decadiene producing a 1:1 mixture of diastereomers and with 1,7-octadiene producing a single diastereomer.