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.

Herein, we report the first efficient platinum-catalysed alkoxycarbonylations of olefins including sterically hindered and functionalized ones. This atom-efficient catalytic transformation provides straightforward access to a variety of valuable esters.

Carbon dioxide capture from air (CO 2 ∼ 400 ppm) on powder Ce 0.8 Zr 0.2 O 2 solid solution and subsequent conversion to dimethyl carbonate is described. The process includes three steps, namely (i) adsorptive enrichment of CO 2 on the oxide surface, (ii) transformation under mild conditions (p = 1 bar; T = 70−110 °C) by subsequent gaseous methanol feeding in inert gas, and (iii) desorptive release of the products by treatment with pure inert gas.

State-of-the-art catalyst systems for hydroxy- and alkoxycarbonylations of olefins make use of palladium complexes. In this work, we report a complementary ruthenium-catalysed hydroxycarbonylation of olefins applying an inexpensive Ru-precursor (Ru3(CO)12)...

An ew class of palladium catalysts,b ased 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 a,bunsaturated 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,a nd amide) furnish the desired carbonylation products smoothly in high yields. Scheme 1. a) Ligand modification and b) design of DPMPhos ligands. Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.Scheme 5. Synthetisis of substituted cyclopentanones in one pot. [a] At 90 8 8Cins tep 1. [b] With 10 mol % p-TsOH instead of HOTfinstep 2. Tf = trifluoromethanesulfonyl. Scheme 6. Synthetisis of g-keto ester.