Kattamuri, Padmanabha V.Yin, JunSiriwongsup, SurachedKwon, Doo-HyunEss, Daniel H.Li, QunLi, GuigenYousufuddin, MuhammedRichardson, Paul F.Sutton, Scott C.Kürti, László2017-11-142017-11-142017Kattamuri, Padmanabha V., Yin, Jun, Siriwongsup, Surached, et al.. "Practical Singly and Doubly Electrophilic Aminating Agents: A New, More Sustainable Platform for Carbon–Nitrogen Bond Formation." <i>Journal of the American Chemical Society,</i> 139, no. 32 (2017) American Chemical Society: 11184-11196. https://doi.org/10.1021/jacs.7b05279.https://hdl.handle.net/1911/98800Given the importance of amines in a large number of biologically active natural products, active pharmaceutical ingredients, agrochemicals, and functional materials, the development of efficient C–N bond-forming methods with wide substrate scope continues to be at the frontier of research in synthetic organic chemistry. Here, we present a general and fundamentally new synthetic approach for the direct, transition-metal-free preparation of symmetrical and unsymmetrical diaryl-, arylalkyl-, and dialkylamines that relies on the facile single or double addition of readily available C-nucleophiles to the nitrogen atom of bench-stable electrophilic aminating agents. Practical single and double polarity reversal (i.e., umpolung) of the nitrogen atom is achieved using sterically and electronically tunable ketomalonate-derived imines and oximes. Overall, this novel approach represents an operationally simple, scalable, and environmentally friendly alternative to transition-metal-catalyzed C–N cross-coupling methods that are currently used to access structurally diverse secondary amines.engThis is an author's peer-reviewed final manuscript, as accepted by the publisher. The published article is copyrighted by the American Chemical Society.Journal articleFINAL_REVISED_JACS_Nitrogen_Linchpin_and_Umpolung_Manuscript_June_24_2017https://doi.org/10.1021/jacs.7b05279