NiH-catalyzed C-N bond formation: insights and advancements in hydroamination of unsaturated hydrocarbons

• Published in: Chemical science (Cambridge) Vol. 15; no. 2; pp. 442 - 457
• Main Authors: Lee, Changseok, Kang, Hyung-Joon, Hong, Sungwoo
• Format: Journal Article
• Language: English
• Published: England Royal Society of Chemistry 03.01.2024; The Royal Society of Chemistry
• Subjects: Alkenes; Alkynes; Catalysis; Chemical bonds; Chemical reactions; Chemical synthesis; Chemistry; Functional groups; Metal hydrides; Nickel; Organometallic compounds; Reaction mechanisms; Reagents; Substrates
• ISSN: 2041-6520; 2041-6539
• DOI: 10.1039/d3sc05589b

The formation of C-N bonds is a fundamental aspect of organic synthesis, and hydroamination has emerged as a pivotal strategy for the synthesis of essential amine derivatives. In recent years, there has been a surge of interest in metal hydride-catalyzed hydroamination reactions of common alkenes and alkynes. This method avoids the need for stoichiometric organometallic reagents and overcomes problems associated with specific organometallic compounds that may impact functional group compatibility. Notably, recent developments have brought to the forefront olefinic hydroamination and hydroamidation reactions facilitated by nickel hydride (NiH) catalysis. The inclusion of suitable chiral ligands has paved the way for the realization of asymmetric hydroamination reactions in the realm of olefins. This review aims to provide an in-depth exploration of the latest achievements in C-N bond formation through intermolecular hydroamination catalyzed by nickel hydrides. Leveraging this innovative approach, a diverse range of alkene and alkyne substrates can be efficiently transformed into value-added compounds enriched with C-N bonds. The intricacies of C-N bond formation are succinctly elucidated, offering a concise overview of the underlying reaction mechanisms. It is our aspiration that this comprehensive review will stimulate further progress in NiH-catalytic techniques, fine-tune reaction systems, drive innovation in catalyst design, and foster a deeper understanding of the underlying mechanisms. This review highlights recent progress in NiH-catalyzed hydroamination, focusing on its application to a variety of alkenes and alkynes.