Ring-Walking of Zerovalent Nickel on Aryl Halides

Bilbrey, Jenna A.; Bootsma, Andrea N.; Bartlett, Marcus A.; Locklin, Jason; Wheeler, Steven E.; Allen, Wesley D.

doi:10.1021/acs.jctc.6b01143

Cited by 22 publications

(21 citation statements)

References 52 publications

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“…Ring-walking of Ni(dppp) and the corresponding oxidative addition of 1-bromo-2-methylbenzene (solid red, X = C–CH 3 ) and 2-bromopyridine (dashed blue, X = N); energies are given relative to the separated catalyst and substrate and were computed at the B3LYP-D3/TZ2P&LANL2TZ-(f)&LANL08d level of theory. Adapted from ref (635). Copyright 2017 American Chemical Society.…”

Section: Mechanistic Complexity In Catalysis By 3d Transition Metalsmentioning

confidence: 99%

Computational Approach to Molecular Catalysis by 3d Transition Metals: Challenges and Opportunities

et al. 2018

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Computational chemistry provides a versatile toolbox for studying mechanistic details of catalytic reactions and holds promise to deliver practical strategies to enable the rational in silico catalyst design. The versatile reactivity and nontrivial electronic structure effects, common for systems based on 3d transition metals, introduce additional complexity that may represent a particular challenge to the standard computational strategies. In this review, we discuss the challenges and capabilities of modern electronic structure methods for studying the reaction mechanisms promoted by 3d transition metal molecular catalysts. Particular focus will be placed on the ways of addressing the multiconfigurational problem in electronic structure calculations and the role of expert bias in the practical utilization of the available methods. The development of density functionals designed to address transition metals is also discussed. Special emphasis is placed on the methods that account for solvation effects and the multicomponent nature of practical catalytic systems. This is followed by an overview of recent computational studies addressing the mechanistic complexity of catalytic processes by molecular catalysts based on 3d metals. Cases that involve noninnocent ligands, multicomponent reaction systems, metal–ligand and metal–metal cooperativity, as well as modeling complex catalytic systems such as metal–organic frameworks are presented. Conventionally, computational studies on catalytic mechanisms are heavily dependent on the chemical intuition and expert input of the researcher. Recent developments in advanced automated methods for reaction path analysis hold promise for eliminating such human-bias from computational catalysis studies. A brief overview of these approaches is presented in the final section of the review. The paper is closed with general concluding remarks.

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Section: Mechanistic Complexity In Catalysis By 3d Transition Metalsmentioning

confidence: 99%

Computational Approach to Molecular Catalysis by 3d Transition Metals: Challenges and Opportunities

et al. 2018

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“…Further calculations were undertaken to model the ringwalking [38][39][40][41][42] step, using 2a-Br and 3-Br as substrates. In each case, three h 2 -complexes are linked by two transition states, leading from the carbonyl group to the halide site ( Fig.…”

Section: Computational Modelling Of Ring Walking and Oxidative Additionmentioning

confidence: 99%

Aldehydes and ketones influence reactivity and selectivity in nickel-catalysed Suzuki–Miyaura reactions

et al. 2020

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“…We have shown that aryl aldehydes and ketones can displace ligands such as COD from a Ni 0 center. The resulting selectivity is likely due to a subsequent 'ring-walking' process, [31][32][33][34][35] as selectivity is only obtained when the aryl halide site is in conjugation with the aldehyde or ketone. This coordination behavior results in selectivity in catalytic cross-coupling reactions, to the extent that the normal order of reactivity of aryl halides (I > Br > Cl) is changed substantially.…”

Section: Discussionmentioning

confidence: 99%

Aldehydes and Ketones Influence Reactivity and Selectivity in Nickel-Catalyzed Suzuki-Miyaura Reactions

Cooper¹,

Léonard²,

Bajo³

et al. 2019

Preprint

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We show that the energetically-favorable coordination of aldehydes and ketones – but not esters – to nickel(0) during Suzuki-Miyaura reactions can lead either to exquisite selectivity and enhanced reactivity, or to the inhibition of the reaction. Aryl halides where the C-X bond is connected to the same π-system as an aldehyde or ketone functional group undergo unexpectedly rapid oxidative addition, and are selectively cross-coupled during inter- and intramolecular competition reactions. When aldehydes and ketones are present elsewhere, such as in the form of exogenous additives, the cross-coupling reaction is inhibited depending on how strongly the pendant carbonyl group can coordinate to nickel(0). This work advances our understanding of how common functional groups interact with nickel(0) catalysts, and presents synthetic chemists with a tool that can be used to achieve site-selectivity in functionalized molecules.

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Ring-Walking of Zerovalent Nickel on Aryl Halides

Cited by 22 publications

References 52 publications

Computational Approach to Molecular Catalysis by 3d Transition Metals: Challenges and Opportunities

Computational Approach to Molecular Catalysis by 3d Transition Metals: Challenges and Opportunities

Aldehydes and ketones influence reactivity and selectivity in nickel-catalysed Suzuki–Miyaura reactions

Aldehydes and Ketones Influence Reactivity and Selectivity in Nickel-Catalyzed Suzuki-Miyaura Reactions

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