Thursday 23 May 2013

Synthetic Uses of Ammonia in Transition-Metal Catalysis

Synthetic Uses of Ammonia in Transition-Metal Catalysis (pages 3201–3213)

European Journal of Organic Chemistry

Jinho Kim, Hyun Jin Kim and Sukbok Chang
DOI: 10.1002/ejoc.201300164

Although ammonia (NH₃) is a cheap, abundant, and readily available nitrogen source, it has rarely been used in transition-metal catalysis, due to several obstacles. However, significant advances in the metal-mediated utilization of ammonia have been made recently. This review presents the most recent examples in metal-mediated amination and other relevant reactions with ammonia or ammonium salts.
http://onlinelibrary.wiley.com/doi/10.1002/ejoc.201300164/abstract

Ammonia (NH₃) is a cheap, abundant, and readily available nitrogen source, being one of the chemicals produced in the greatest quantities. Whereas ammonia is utilized mainly as a feedstock for the production of fertilizers, it is also employed in industry as a component of various nitrogen-containing compounds. In metal catalysis, in contrast, ammonia has been used only with limited success, due to several difficulties such as generation of stable Lewis acid-base adducts, facile ligand exchange for ammonia in active metal complexes, a propensity towards undesired second transformations of initially formed species, and the requirement for special equipment to run the reactions. Despite these obstacles, the direct use of ammonia in catalysis has continuously attracted great interest, leading recently to significant progress. Whereas liquid or gaseous ammonia were most commonly employed in the past, under harsh conditions, notable catalytic reactions using easy-to-handle ammonium salts under milder and more convenient conditions have now been developed. In this review we briefly describe the most recent examples of transition-metal-catalyzed reactions using ammonia or ammonium salts.