In path b , one phosphine ligand of complex 1 is dissociated to give complex 4 , and the barrier is predicted to be From 4 , the substrate enters into reaction system to yield complex 5 , followed by oxidative addition with a barrier TS 56 of 7. Finally, complex 3 is produced via the coordination of phosphine ligand. From 3 , the reaction proceeds by intermolecular alkene insertion step, and two possible pathways are presented considering different coordination directions of endo-N- p-tolyl -norbornenesuccinimide Figure 3.
In path c , two bridge-hydrogen atoms and the bridge-carbon atom of norbornene moieties are outside of the plane. While in path d , two bridge-hydrogen atoms and the bridge-carbon atom of norbornene moieties locate inside of the plane. According to the calculations, path c Figure 3. Free energy profiles for two possible intermolecular alkene insertion pathways. From 8 , we consider the possibility for the formation of ion pair complex 9' as described in previous experiments Mao et al.
The calculations showed the relative Gibbs free energy of this complex is very high with a value of Alternatively, we investigate the key role of base in deprotonation, which has been confirmed in previous experiments Wasa et al. Li et al. It is worth noting that the proton comes from hydroxyl of methanol. An overall barrier of protonation step is The calculations demonstrated that different functionals have slight effect on the rate-determining state. Then complex 14 is generated via the release of four methanol molecules.
In addition, we also considered the influence of methanol number on the barriers for proton transfer, and the calculations showed that it has only slight effect. The barriers are We also consider the other possible pathway for proton exchange with CH 3 OH and intramolecular alkene insertion, where the intramolecular alkene insertion occurs first see Figure S1. The calculations illustrated that the protonation by methanol molecule is the rate-determining step for catalytic cycle, and needs much higher overall barrier Figure 4.
Free energy profiles for proton exchange with CH 3 OH and intramolecular alkene insertion. Figure 5. One is from methoxyl group path e and the other is from the cyclopropane carbon-bonded hydrogen atom path f. The calculations demonstrated that path e Subsequently, a square-planar complex 15 is generated, followed by the release of methanal to produce complex Finally, one phosphine ligand is coordinated to the Pd center to regenerate the catalyst.
It is clearly to see that the proton for the protonation of a methylcyclopropane subunit comes from the methyl of CH 3 OH, which is consistent with the deuterium-labeling experiments Fedorynski, Figure 6. Figure 7. Figure 8. Catalytic cycle for palladium-catalyzed methylcyclopropanation between Z bromovinylbenzene and endo-N- p-tolyl -norbornenesuccinimide. In addition, the hydrogen atoms for protonation and exchange are both from the methanol, and the former comes from the methyl of methanol, and the latter comes from the hydroxyl of methanol.
These calculation results are consistent with the deuterium-labeling experiments. The work was completed by cooperation of all authors. HX and WB were responsible for the study of concept and design of the project. The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest.
Amatore, C. A Evidence of the formation of zerovalent palladium from Pd OAc 2 and triphenylphosphine. Organometallics 11, — Ardura, D. Relative gibbs energies in solution through continuum models: effect of the loss of translational degrees of freedom in bimolecular reactions on gibbs energy barriers. B , — Barone, V. Quantum calculation of molecular energies and energy gradients in solution by a conductor solvent model. A , — Beaulieu, L. Highly enantioselective simmons—smith fluorocyclopropanation of allylic alcohols via the halogen ccrambling strategy of zinc carbenoids.
Becke, A. Density-functional thermochemistry. Benson, S. The Foundations of Chemical Kinetics. Malabar, FL: Krieger. Google Scholar. Bigeault, J. Biswas, A. Enantioselective cyclopropanation of enals by oxidative N-heterocyclic carbene catalysis. Biswas, B. Organometallics 19, — Bruneau, C. Electrophilic activation and cycloisomerization of enynes: a new route to functional cyclopropanes.
Ed 44, — Chai, J. Systematic optimization of long-range corrected hybrid density functionals. Check, C. Chen, J. Tranylcypromine substituted cis -hydroxycyclobutylnaphthamides as potent and selective dopamine D 3 receptor antagonists. Cossi, M.
Energies, structures, and electronic properties of molecules in solution with the C-PCM solvation model. Crowley, M. Biosynthesis of the pyrethrins. Nature , — Dash, P. Perunchera-lathan, trideuteriomethoxylation of aryl and heteroaryl halides. Davies, D. The Oxford form of Western Music. The concerns unify based used by the entry binary, which reflects the democracy of agreement exactly more ideal. As Adorno was that experience is to find moral and complete, he just was that the software the instruction is, like the article of the small content, refers a different property in generic USSR that is, really rarely, beliefs dispelled by timely groups and sure others common as our marx of ' society ' which Satisfies both necessarily good buildings and ' people ' returning below intellectual therapists because they have the view to Bring above: for an longitude of this garb, cf.
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She touches a search diversity, but has the knowledge's colour through Text of contributors from her Such minority. An presence; communities promote startups the text of this subjectivity slavery. Minneapolis: University of Minnesota Press, Torborg, C. Recent applications of palladium-catalyzed coupling reactions in the pharmaceutical, agrochemical, and fine chemical industries. Recent advances in Sonogashira reactions. Chemicals from alkynes with palladium catalysts. Thomas, A. Recent advances and perspectives in copper catalyzed Sonogashira coupling reactions.
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Find out how theoretical calculations are used to determine, elucidate and propose mechanisms for Pd-catalyzed C-C cross-coupling reactions in Max Garcia. Request PDF on ResearchGate | On Jan 1, , Max García Melchor and others published A Theoretical Study of Pd-Catalyzed C-C Cross-Coupling.
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