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WIREs Comput Mol Sci
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Computationally deciphering palladium‐catalyzed reaction mechanisms

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Computational studies receive increased attention in the mechanistic exploration of transition metal catalyzed reactions. Especially in Pd catalysis, numerous mechanistic insights could be gained by the use of computational tools to complement experimental studies in order to provide a more detailed mechanistic picture. This includes not only the exploration of novel mechanistic scenarios, but also the comparison of different plausible reaction pathways. The current intense use of calculations in mechanistic studies of Pd‐catalyzed reactions has encouraged constant advancements in the field. However, a number of challenges will be faced in the computational treatment of Pd reactivities, including tackling conformational space, charged molecules, varying ligation states and the description of complexes bearing multiple Pd centers. Their careful consideration may enrich the mechanistic picture of numerous Pd‐catalyzed reactions, but may also encourage further development of computational methodology. WIREs Comput Mol Sci 2016, 6:226–242. doi: 10.1002/wcms.1244

This article is categorized under:

  • Electronic Structure Theory > Density Functional Theory
Reductive elimination study of a mixed Cl/OAc Pd(III) complex and suggested ligand scrambling mechanism. (Reprinted with permission from Ref . Copyright 2014 The Royal Society of Chemistry)
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Direct versus dissociative pathways in reactivity studies of Pd(III) dimer complexes.
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Pd(I)‐dimer‐mediated reactions via direct oxidative addition at the Pd(I)–Pd(I) framework (Nu = Br, SCF3 , and SeCF3 ). (Reprinted with permission from Ref . Copyright 2015 American Chemical Society)
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Ligation state‐dependent selectivity: (a) the versatile PiPrtBu2 ligand allows for a switch in selectivity from C–Cl to C–OTf via mono‐ and bisligated transition states, respectively; (b) first ever located bisligated transition state for PtBu3.
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Turnover‐limiting intermediates and preferred bisligated reaction pathway in the Suzuki–Miyaura coupling reaction for L = PPh3 and PMe3 (a) and favored monoligated pathway for L = PtBu3 (b). (Reprinted with permission from Ref . Copyright 2015 American Chemical Society)
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Comparison of mono‐ and bisligated oxidative addition pathways for Pd‐catalysts possessing phosphine ligands with different steric requirements. (Reprinted with permission from Ref . Copyright 2015 American Chemical Society)
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Counterion‐directed enantioselectivity in Tsuji–Trost allylation.
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Counterion effect on the regioselectivity of C–H arylation of 2‐substituted thiophenes.
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Additive effect in Stille cross‐coupling: neutral versus anionic oxidative addition.
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Calculated energy barriers for the oxidative addition of Ph–Cl to Pd/SPhos or Pd/XPhos. (Reprinted with permission from Ref . Copyright 2014 The Royal Society of Chemistry)
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The main conformations of the myrtenic acid amide–Ph2P–Pd complex determined by a combination of NMR analysis and DFT calculations.
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The flexible Pd(η3‐cyclohexenyl)‐complexed Trost modular ligand (a), overlay of computationally addressed conformations (b), and favored endo‐conformer obtained from DFT optimization (c).
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