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.

The synthesis of carboxylic acids is of fundamental importance in the chemical industry and the corresponding products find numerous applications for polymers, cosmetics, pharmaceuticals, agrochemicals, and other manufactured chemicals. Although hydroxycarbonylations of olefins have been known for more than 60 years, currently known catalyst systems for this transformation do not fulfill industrial requirements, for example, stability. Presented herein for the first time is an aqueous‐phase protocol that allows conversion of various olefins, including sterically hindered and demanding tetra‐, tri‐, and 1,1‐disubstituted systems, as well as terminal alkenes, into the corresponding carboxylic acids in excellent yields. The outstanding stability of the catalyst system (26 recycling runs in 32 days without measurable loss of activity), is showcased in the preparation of an industrially relevant fatty acid. Key‐to‐success is the use of a built‐in‐base ligand under acidic aqueous conditions. This catalytic system is expected to provide a basis for new cost‐competitive processes for the industrial production of carboxylic acids.

A new class of palladium catalysts, based on heterocyclic diphosphines, was rationally designed and synthesized. Application of one of these catalysts allows novel Markovnikov-selective carbonylation of non-activated alkynes with heteroarenes to give the corresponding branched α,β-unsaturated ketones in excellent yields (up to 97 %) and regioselectivities (b/l up to 99:1). In addition to heteroarenes, other common nucloephiles (alcohol, phenol, amine, and amide) furnish the desired carbonylation products smoothly in high yields.

The synthesis of carboxylica cids is of fundamental importance in the chemical industry and the corresponding products find numerous applications for polymers,c osmetics, pharmaceuticals,a grochemicals,a nd other manufactured chemicals.A lthough hydroxycarbonylations of olefins have been knownf or more than 60 years,c urrently knownc atalyst systems for this transformation do not fulfill industrial requirements,for example,stability.Presented herein for the first time is an aqueous-phase protocol that allows conversion of various olefins,including sterically hindered and demanding tetra-, tri-, and 1,1-disubstituted systems,aswell as terminal alkenes,into the corresponding carboxylic acids in excellent yields.T he outstanding stability of the catalyst system (26 recycling runs in 32 days without measurable loss of activity), is showcased in the preparation of an industrially relevant fatty acid. Key-tosuccess is the use of abuilt-in-base ligand under acidic aqueous conditions.This catalytic system is expected to provide abasis for new cost-competitive processes for the industrial production of carboxylic acids.