Asymmetric catalysis

The use of ammonia as a nitrogen source in catalytic asymmetric reactions is attractive but represents a difficult exercise. Now, the asymmetric synthesis of N-unprotected α-amino esters from α-diazoesters and ammonia is achieved by cooperative action of copper complexes and chiral hydrogen-bond donors.

Making many stereogenic centres in a single step remains a challenge. Now, a combined nickel and copper-catalysed stereodivergent propargylic substitution process has been developed to access four stereoisomers of amathaspiramide D. The scope of the reaction is shown across a range of propargylic carbonate and aldimine ester substrates to generate a number of chiral propargylated α-amino ester products.

Asymmetric construction of alkyl C–C bonds with good stereocontrol of the two connecting carbons, particularly when using alkenes as feedstocks, is challenging. Here, the authors show a catalytic method to form multiple adjacent carbon stereocentres in a single operation.

The catalytic asymmetric benzylations of prochiral nucleophiles are very limited. Here, the authors disclose an asymmetric α−benzylation of N-unprotected amino acids with benzyl alcohol derivatives by a chiral aldehyde-involved catalytic system.

Migratory alkene isomerizations and cross-coupling reactions are both possible under nickel catalysis, but usually require different conditions. Here the authors show a combined protocol to isomerize a double bond and then, via an in-situ exchange of ligands, perform an enantioselective C(sp2)–C(sp3) cross-coupling.

The construction of vicinal, congested stereocenters with high selectivities is of general utility in chemistry. Here the authors report a doubly-stereoconvergent, Cu/Mg-catalyzed asymmetric propargylic substitution reaction to convert simple starting materials to products with vicinal tertiary and all-carbon quaternary stereocenters in high yields and excellent diastereo- and enantioselectivities