New Palladium Complexes with S- or Se-Containing Schiff-Base Ligands as Efficient Catalysts for the Suzuki—Miyaura Cross-Coupling Reaction of Aryl Bromides with Phenylboronic Acid under Aerobic Conditions.

Amidation of 1'-(diphenylphosphanyl)ferrocene-1-carboxylic acid (Hdpf) with ethane-1,2-diamine afforded N,N'-ethylenebis[1'-(diphenylphosphanyl)ferrocene-1-carboxamide] (1), which was isolated in free and solvated form, 1·2AcOH. Both 1 and Hdpf were further converted to their respective phosphane sulfides, 2·2AcOH and 3 that were structurally characterized. Testing of the amidophosphane ligands in Suzuki-Miyaura cross-coupling reaction between phenylboronic acid and various aryl halides revealed that catalyst formed in situ from 1 and palladium(II) acetate is highly active in coupling reactions of aryl bromides whilst the corresponding aryl chlorides showed no or only poor conversions. The catalyst based on 2·2AcOH gave markedly lower yields of the coupling products.

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A phosphine-free, atom-efficient cross-coupling reaction of triorganoindiums with acyl chlorides catalyzed by immobilization of palladium(0) in MCM-41

RSC Advances ◽

10.1039/c7ra08355f ◽

2017 ◽

Vol 7 (67) ◽

pp. 42570-42578 ◽

Cited By ~ 3

Author(s):

Jiankang Miao ◽

Bin Huang ◽

Haiyi Liu ◽

Mingzhong Cai

Keyword(s):

Schiff Base ◽

Schiff Base Complex ◽

Coupling Reaction ◽

Cross Coupling ◽

Free Atom ◽

Acyl Chlorides ◽

Base Complex ◽

Cross Coupling Reaction ◽

Mcm 41

The phosphine-free, atom-efficient cross-coupling of triorganoindiums with acyl chlorides has been achieved using a recyclable MCM-41-immobilized palladium(0)–Schiff base complex.

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A Quantum-Chemical DFT Approach to Elucidation of the Chirality Transfer Mechanism of the Enantioselective Suzuki–Miyaura Cross-Coupling Reaction

Journal of Chemistry ◽

10.1155/2017/3617527 ◽

2017 ◽

Vol 2017 ◽

pp. 1-12 ◽

Cited By ~ 3

Author(s):

Radomir Jasiński ◽

Oleg M. Demchuk ◽

Dmytro Babyuk

Keyword(s):

Quantum Chemical ◽

Coupling Reaction ◽

Cross Coupling ◽

Palladium Complexes ◽

Initial Reaction ◽

Chiral Ligand ◽

Chirality Transfer ◽

Cross Coupling Reaction ◽

Enantioselective Reactions ◽

Selection Of

The DFT calculations of the simplified model of the asymmetric Suzuki–Miyaura coupling reaction were performed at the M062x/LANL2DZ theory level at first. It was found that enantioselective reactions mediated by the palladium complexes of chiral C,P-ligands follow a four-stage mechanism similar to that proposed previously as one of the most credible mechanisms. It should be underlined that the presence of substituents in the substrates and the chiral ligand at ortho positions determines the energies of possible diastereoisomeric transition states and intermediates in initial reaction steps. This suggests that, in practice, a sharp selection of theoretically possible paths of chirality transfer from the catalyst to the product should have a place and, therefore, the absolute configuration of the formed atropisomeric product is defined and can be predicted.

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