Direct reductive amination of a wide range of ketones has been accomplished by the cooperative catalysis of an Ir(III)-diamine complex and a chiral phosphoric acid or its conjugate base.

When combined with a chiral phosphate counteranion, a chiral diamine-ligated Ir(III) catalyst displayed excellent enantioselectivities in the asymmetric hydrogenation of a wide range of acyclic imines, affording chiral amines in up to 99% ee.

Imines can be reduced to afford synthetically important amines via a number of means, of which half-sandwich metal complex-effected reduction has gained particular prominence in the past one decade or so. This Feature Article aims to summarise the progress made with such metal catalysts, placing emphasis on our own work. The article covers transfer hydrogenation and hydrogenation, and finishes with a brief account of catalyst immobilisation and mechanistic understanding.

A series of laboratory themed simulations developed by Learning Science Ltd. were integrated into a first year laboratory module at the University of Leicester. These simulations allow students to attempt the experiments they will do in the laboratory in a risk-free way that provides the opportunity to make mistakes and learn how to correct them using the immediate feedback generated. High student engagement was observed during our pilot, and student end-of-module comments were very positive for this technological enhancement.

Experimental and DFT studies show the selectivity of C–H bond activation at [MCl2Cp*]2 (M = Ir, Rh) species can be controlled by the choice of metal catalyst, reflecting kinetic control at M = Ir and thermodynamic control at M = Rh.

A series of chiral iridacycles have been synthesised and shown to be moderately enantioselective in asymmetric transfer hydrogenation reactions.

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Detailed experimental and computational studies have been carried out on the oxidative coupling of the alkenes C2H3Y (Y=CO2Me (a), Ph (b), C(O)Me (c)) with 3-aryl-5-R-pyrazoles (R=Me (1 a), Ph (1 b), CF3 (1 c)) using a [Rh(MeCN)3Cp*][PF6]2/Cu(OAc)2⋅H2O catalyst system. In the reaction of methyl acrylate with 1 a, up to five products (2 aa–6 aa) were formed, including the trans monovinyl product, either complexed within a novel CuI dimer (2 aa) or as the free species (3 aa), and a divinyl species (6 aa); both 3 aa and 6 aa underwent cyclisation by an aza-Michael reaction to give fused heterocycles 4 aa and 5 aa, respectively. With styrene, only trans mono- and divinylation products were observed, whereas with methyl vinyl ketone, a stronger Michael acceptor, only cyclised oxidative coupling products were formed. Density functional theory calculations were performed to characterise the different migratory insertion and β-H transfer steps implicated in the reactions of 1 a with methyl acrylate and styrene. The calculations showed a clear kinetic preference for 2,1-insertion and the formation of trans vinyl products, consistent with the experimental results.