Catalytic Organometallic Reactions of Ammonia

Abstract

Until recently, ammonia had rarely succumbed to catalytic transformations with homogeneous catalysts, and the development of such reactions that are selective for the formation of single products under mild conditions has encountered numerous challenges. However, recently developed catalysts have allowed several classes of reactions to create products with nitrogen-containing functional groups from ammonia. These reactions include hydroaminomethylation, reductive amination, alkylation, allylic substitution, hydroamination, and cross-coupling. This Minireview describes examples of these processes and the factors that control catalyst activity and selectivity.

Alkyne hydroamination triggered cyclizations: A powerful tool for the construction of biologically important structural motifs

“…Catalytic hydroamination of alkynes with ammonia [53] is supposed to be a difficult task for several reason; for instance: (1) the catalyst is often deactivated by formation of stable Werner ammine complexes (2) the strength of the NeH bond in ammonia (107 kcal mol À1 ) makes "NeH activation" by the metal center challenging (3) the moderate basicity and low acidity of ammonia disfavor proton exchange. A major breakthrough in this area has been achieved recently.…”

Synthesis, characterization and catalytic activity of gold complexes with pyridine-based selone ligands

“…Moreover, the catalytic activities using gold complexes with selone ligands are better than those of gold complexes with thione ligands [38] and HAuCl 4 . Then, the complex 3 was chosen as the optimal catalyst to screen the various solvents (Table 3, entries [8][9][10][11][12]. High yield of 95% of the desired products was achieved within 3 h in water solvent.…”

“…Therefore, a variety of protocols for synthesizing functionalized anilines have been developed [7][8][9][10][11][12][13][14][15][16][17][18][19]. The desirable method for the synthesis of functionalized anilines is the reduction of nitroarenes using transition metal catalysts in the presence of sodium tetrahydroborate (NaBH 4 ) [20].…”

Hydroaminomethylation of the Renewable Limonene with Ammonia in an Aqueous Biphasic Solvent System

“…A review from Hartwig and Klinkenberg provides a short overview of the use of ammonia as substrate in hydroaminomethylation and related reactions [16]. Recently, we reported about hydroaminomethylations with various starting materials as isoprene [17], cyclopentadiene [18], long-chain alkenes [19], and fatty acids [20,21] in biphasic as well as thermomorphic solvent systems [22,23].…”