Computational modelling of Pd-catalysed alkoxycarbonylation of alkenes and alkynes

Abstract

This perspective highlights the computational modeling of alkene and alkyne alkoxycarbonylation at palladium catalysts. We cover studies on Pd–catalysed alkoxycarbonylation of alkenes with bidentate diphosphine ligands, which reveal a hydride...

Insights into the ruthenium-catalysed selective reduction of cardanol derivatives via transfer hydrogenation: a density functional theory study

“…The η 3 -allyl complexes tend to be stable thermodynamic sinks on the PES and thus require significant activation for further reaction. [53][54][55] Here, we used two equivalents of explicit iPrOH to reduce the two double bonds. Slippage from the η 3 -allyl bonding mode to a η 1 -allyl bonding mode with a Ru-C sigma bond (with carbon#11) helps create room for the incoming solvent molecules forming 6 (ΔG 56 = 15.4 kcal mol −1 ).…”

“…91 This level has performed very well in a number of studies from our group. [52][53][54][55][56][57]…”

“…To saturate the coordination sphere around the metal and activate the double bonds for subsequent reductions, it was assumed that Ru forms an intramolecular chelate complex with η 4coordination of the polyene tail to the metal, affording complex 1 in Scheme 2b. Starting from this intermediate and using a DFT protocol that has been applied fruitfully to several reaction catalysed by metals from the second transition row, [52][53][54][55][56][57] we have now traced complete catalytic cycles leading to the main products. The cycle is divided into several steps, focusing first on the isomerisation of the double bonds, then the reduction to the diene cardanol, followed by reduction to the monoene cardanol.…”

In Silico Investigation of Palladium‐Catalyzed Chemoselective Monoalkoxycarbonylation of 1,3‐diynes for Conjugated Enynes Synthesis

“…Mechanistic studies for the Pd-catalysed alkyne alkoxycarbonylation with P,N-chelating ligands revealed that an in situ base mechanism is operating. [14] As a representative example, Beller and coworkers reported palladium complex with two hemilabile P,Nligands for the alkoxycarbonylation of internal olefins. [15] The computational studies for this reaction have been reported by Tian [16] and our groups.…”

(In situ) spectroscopic studies on state-of-the-art Pd(ii) catalysts in solution for the alkoxycarbonylation of alkenes

“…Theoretical studies by Bühl et al using DFT methods on alkyne alkoxycarbonylations with Pd catalysts incorporating hemilabile (Ph 2 PIJ2-Py)) ligands did unravel the elementary steps of the catalytic cycle. [36][37][38] Proton shuttling by the pyridyl groups in the initiation and termination steps have been found to be crucial in this mechanism. In the initiation step, the pyridyl group functions first as an in situ base and when protonated as an in situ acid, which protonates the coordinated alkyne followed by CO insertion.…”