Search

An efficient palladium-manganese system for the Markovnikov selective alkoxycarbonylation reaction of aromatic and aliphatic alkenes was developed. [Display omitted] • A general and efficient palladium-manganese system for the Markovnikov selective alkoxycarbonylation reaction of alkenes. • By using the carbazole-derived phosphine ligand containing bipyridine moiety, various aromatic and aliphatic olefins were transformed into the corresponding esters in good yields with moderate to high branched selectivity. • Preliminary mechanistic studies reveal the respective contribution of palladium and manganese centers to achieve highly branch-selective alkoxycarbonylations. Carbazole derived phosphine ligands containing pyridine moiety were designed and prepared. It allows the challenging Pd-catalyzed Markovnikov-selective alkoxycarbonylation of aliphatic alkenes to give the branched ester products (28 examples; 51–97% branch selectivity). Preliminary mechanistic studies support that the bridging bromide between Pd and Mn centers is crucial for the enhancement of regioselectivity. [ABSTRACT FROM AUTHOR]

Catalytic carbonylations of alkynes represent straightforward and atom-economic synthesis of α,β-unsaturated carbonyl compounds. One of the issues associated with the currently known catalytic systems is insufficient efficiency. In this context, Pd/ligand-catalyzed regioselective and efficient alkoxycarbonylation of terminal alkynes is desirable for the synthesis of α,β-unsaturated esters. Herein, we present the use of a newly designed bifunctional ligand for efficient Pd-catalyzed alkoxycarbonylation of alkynes. Both aliphatic and aromatic alkynes were smoothly transformed to the branched desired products with high selectivity (28 examples, 45–96% yields, 95.0–99.9% selectivity). [ABSTRACT FROM AUTHOR]