Phosphine‐Free, Efficient Double Carbonylation of Aryl Iodides with Amines Catalyzed by Water‐Insoluble and Water‐Soluble N‐Heterocyclic Carbene–Amine Palladium Complexes

Abstract

The water-insoluble and water-soluble Nheterocyclic carbene (NHC)-amine palladium complexes, Ipr-PdA C H T U N G T R E N N U N G (deba)Cl and SO 3 -Ipr-PdA C H T U N G T R E N N U N G (deba)Cl, were synthesized. Both catalysts exhibit excellent activity in the phosphine-free double carbonylation of aryl iodides with amines to produce a-keto amides. Moreover, as the water-soluble catalyst exhibits significant compatibility in the aqueous phase with the activities of different Pd-NHC complexes, we con-clude that the intramolecular amine ligand strongly affects the selectivity of the products in double carbonylation reaction and serves as an alternative of phosphine ligands.

A comparative study of biradicaloids as ligands in iron tetracarbonyl complexes

“…38 1,2-Bis(2,6-diisopro-pylphenylimino)ethane was synthesized from 1,3-bis(2,6-diisopropylphenyl)amine according to literature procedures. 39 Fe(CO)5 (Sigma Aldrich, trace metal basis), Fe2(CO)9, Fe3(CO)12 and Ph3SiCl (all abcr GmbH) were bought and used as received. 1 H NMR spectra were recorded on Bruker spectrometers operating at 200, 300, 400 or 500 MHz; 13 13 C NMR chemical shifts are reported relative to SiMe4 using the 1 H (residual) and 13 C chemical shifts of the solvent as a secondary standard (C6D6: δ 7.16 for 1 H, δ 128.06 for 13 C; CD2Cl2: δ 5.32 for 1 H, δ 53.50 for 13 C).…”

Robust Acenaphthoimidazolylidene Palladacycles: Highly Efficient Catalysts for the Amination of N‐Heteroaryl Chlorides

“…(entry 13, Table ). When palladacycle 6 , an IPr analogue of palladacycle 3 a , was utilized, only 58 % yield was observed, which further confirmed that ylidenes derived from acenaphthoimidazolium salts showed better catalytic activity than their imidazolium analogues owing to their stronger σ‐donor and weaker π‐acceptor properties.…”

Palladium‐Catalyzed Aerobic Oxidative Carbonylation of C–H Bonds in Phenols for the Synthesis of p‐Hydroxybenzoates

“…Transition‐metal‐catalyzed carbonylation of aryl halides or pseudohalides, established in 1974 by Heck and co‐workers, has served as a most potent methodology for the synthesis of carboxylic acids and their derivatives. On the other hand, activation of inert C–H bonds is a very attractive but difficult goal in synthetic chemistry; however, with the correct selection of catalyst and substrate it can be achieved Even so, carbonylation of C–H bonds presents a great challenge and is an attractive field.…”