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A copper-catalyzed Mannich-type oxidative β-functionalization reaction of amines has been developed. In the presence of an oxidant and a copper catalyst, tertiary amines reacted with N-tosylimines, providing synthetically important 1,3-diamines and enamines, respectively. Preliminary mechanistic studies suggested that the oxidation of the tertiary amine to the enamine intermediate triggers subsequent Mannich-type reactions with N-tosylimines and thus enables the direct β-functionalization of the tertiary amines. [ABSTRACT FROM AUTHOR]

An iridium complex with a newly prepared chiral spiro amino-phosphine ligand efficiently catalyzed the hydrogenation of both β-aryl-β-methyl-nitroalkenes and β-alkyl-β-methyl-nitroalkenes to the corresponding saturated nitroalkanes, which represents the first report of a chiral catalyst that exhibits high enantioselectivity for the challenging hydrogenation of β,β-dialkyl-nitroalkenes. [ABSTRACT FROM AUTHOR]

An asymmetric carbenoid insertion into S–H bonds catalyzed by copper–chiral spiro bisoxazoline complexes has been developed, in which a series of α-mercaptoesters were produced in high yields with moderate to good enantioselectivities (up to 85% ee); this result represents the best enantioselectivity in the catalytic asymmetric carbenoid S–H bond insertion reaction. [ABSTRACT FROM AUTHOR]

Transition-metal-catalysed carbene insertion reaction is a straightforward and efficient protocol for the construction of carbon-carbon or carbon-heteroatom bonds. Compared to the intensively studied and well-established "common" carbene insertion reactions, including carbene insertion into C-H, Si-H, N-H, O-H, and S-H bonds, several "uncommon" carbene insertion reactions, including carbene insertion into B-H, Sn-H, Ge-H, P-H, F-H, C-C, and M-M bonds, have been neglected for a long time. However, more and more studies on uncommon carbene insertion reactions have been disclosed recently, and clearly demonstrate the great synthetic potential of these reactions. The current perspective reviews the history and the newest advances of uncommon carbene insertion reactions, discusses their potential applications and challenges, and also presents an outlook of this promising field., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Modular chiral dendrimers with monodentate phosphoramidite ligands located at the core were synthesized and applied in the Rh-catalyzed asymmetric hydrogenations, afforded unprecedented enhancement of enantioselectivity.

The chiral diphosphinite ligand derived from (R)-1,1'-spirobiindane-7,7'-diol has been found to be highly effective in the Ir-catalyzed asymmetric hydrogenation of quinolines with high substrate/catalyst ratio (up to 5000) and high enantioselectivity (up to 94% ee).