Markovnikov versus anti‐Markovnikov addition and C–H activation: Pd–Cu synergistic catalysis

Abstract

Copper-and palladium-mediated transmetalation and coupling reactions are the backbone to several synthetic methodologies in organic chemistry for CC bond formation. Computer-aided simulations using density functional theory (DFT) (B3LYP-D3 functional with 6-31G** and effective core potential (ECP)-LACVP** for heavy atoms for optimizations and cc-pVTZ(−f) and ECP-LACV3P** for single-point calculations) was used to shed light on the probable mechanism of a novel synergistic Cu/Pd catalysts for the coupling of alkene, (Bpin)2 (where, pin = pinacolate), and vinyl-or aryl-halogenated analogues. Every single conceivable pathway was carefully contemplated, and the base minimum energy pathway was found effectively. The copper-catalyzed nucleophilic generation yields anti-Markovnikov product using styrene as an alkene. This study affirms quantitatively and accurately how the reaction proceeds and at which steps of the synergistic catalysis the demand of the transmetalation and nucleophile formation for the CC coupling using phosphine ligands arise. We conclude that the E and Z selectivity depends on the stereochemistry of the substrates used.

Adsorption Behavior of an Adamantane Derivative on Metal Clusters – DFT Simulation Studies

“…DFT method is used to nd the interaction of APT with Ag/Au/Cu metal clusters (mC) with M06-2X/6-311++G(d,p) (drug)/LANL2DZ (Au Ag, Cu) method/basis set (Fig. 1) [19][20][21][22]. The adsorption energy E = E APT-mC -E mC -E APT , where E APT-mC , E mC , E AMT are energies of APT-mC, mC and APT, respectively [23,24].…”

Computational studies of the CuAAC reaction mechanism with diimine and phosphorus ligands for the synthesis of 1,4-disubstituted 1,2,3-triazoles

“…The C-N outer distances with all ligands that appear in the form of a green-brown disk are within the van der Waals radius. 62,63…”