Mechanistic studies of the catalyst [Pd2(dba)3/1,1′-bis(tert-butyl(pyridin-2-yl)phosphanyl)ferrocene, L2] for olefin alkoxycarbonylation reactions are described.

A silver catalysed synthesis of 6-acyl phenanthridines by oxidative radical decarboxylation-cyclization of α-oxocarboxylates and isocyanides was developed. This reaction provided a novel method to realize C1 insertion via a radical process and various functional groups were well-tolerated.

A general and efficient protocol for iso-selective aminocarbonylation of olefins with aliphatic amines has been developed for the first time. Key to the success for this process is the use of a specific 2-phosphino-substituted pyrrole ligand in the presence of PdX (X=halide) as a pre-catalyst. Bulk industrial and functionalized olefins react with various aliphatic amines, including amino-acid derivatives, to give the corresponding branched amides generally in good yields (up to 99 %) and regioselectivities (b/l up to 99:1).

A general palladium-catalyzed synthesis of linear esters directly from sec- and tert-alcohols is described. Compared to the classic Koch-Haaf reaction, which leads to branched products, this new transformation gives the corresponding linear esters in high yields and selectivity. Key for this protocol is the use of an advanced palladium catalyst system with L2 (py bpx) as the ligand. A variety of aliphatic and benzylic alcohols can be directly used and the catalyst efficiency for the benchmark reaction is outstanding (turnover number up to 89 000).

A selective ruthenium-catalyzed water–gas shift/hydroformylation of internal olefins and olefin mixtures is reported. This novel domino reaction takes place through a catalytic water–gas shift reaction, subsequent olefin isomerization, followed by hydroformylation and reductive amination. Key to the success for the efficient one-pot process is the use of a specific 2-phosphino-substituted imidazole ligand and triruthenium dodecacarbonyl as precatalyst. Industrially important internal olefins react with various amines to give the corresponding tertiary amines generally in good yield and selectivity. This reaction sequence constitutes an economically attractive and environmentally favorable process for the synthesis of linear amines.

A three-component alkoxycyanomethylation of alkenes is achieved using the iridium photoredox catalyst [fac-IrA C H T U N G T R E N N U N G (ppy) 3 ]. This catalytic radical difunctionalization accomplishes both alkylation and alkoxylation of alkenes in one pot. Various alcohols can serve as the alkoxy sources in this transformation. In addition, the introduced cyano group can undergo further transformations into various useful functional groups.

An organocatalyzed aerobic benzylic C–H oxidation of alkyl and aryl heterocycles has been developed. This transition metal-free method is able to overcome the electron-withdrawing effect as well as product-inhibition effects in heterobenzylic radical oxidation. A variety of ketones bearing N-heterocyclic groups could be prepared under relatively mild conditions with moderate to high yields.

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