Hydroamination, Aminoboration, and Carboamination with Electrophilic Amination Reagents: Umpolung-Enabled Regio- and Stereoselective Synthesis of N‑Containing Molecules from Alkenes and Alkynes

• Published in: Journal of the American Chemical Society Vol. 144; no. 2; pp. 648 - 661
• Main Authors: Hirano, Koji, Miura, Masahiro
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 19.01.2022
• Subjects: alkenes; alkynes; amination; catalytic activity; Lewis acids; nitrogen; organic chemistry; reaction mechanisms; stereoselective synthesis
• ISSN: 0002-7863; 1520-5126; 1520-5126
• DOI: 10.1021/jacs.1c12663

Nitrogen (N) is ubiquitously found in bioactive molecules, pharmaceutical agents, and organic functional materials. Accordingly, development of new C–N bond-forming catalysis has been one of the long-standing research subjects in synthetic organic chemistry. In this Perspective, recent advances in highly selective amination reactions with electrophilic amination reagents are described: by taking advantage of the concept of nitrogen umpolung, otherwise challenging aminofunctionalizations, such as hydroamination, aminoboration, and carboamination, of readily available feedstock-like alkenes and alkynes are possible, giving densely functionalized complex and often chiral alkylamines with high selectivity. The scope, limitations, and reaction mechanism are briefly summarized.