Non-innocent Additives in a Palladium(II)-Catalyzed C–H Bond Activation Reaction: Insights into Multimetallic Active Catalysts

Anand, Megha; Sunoj, Raghavan B.; Schaefer, Henry F.

doi:10.1021/ja412770h

Cited by 122 publications

(82 citation statements)

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“…A similar bimetallic Pd−Ag complex was also discussed in the context of ortho C−H activation by Sunoj and Schaefer in 2014. 273 The preference for meta-selective C−H activation was also studied in 2011 by Zhang et al at the CPCM (benzene) B3LYP/6-311+G(d,p)(SDD)//B3LYP/6-31G(d)-(LANL2DZ) level theory (Scheme 15b). 274 They summarized that steric repulsion between a pyridine ligand and substrate directs the reaction to the meta position and in some cases, due to electronic effects, to para C−H activation.…”

Section: C−h Bond Activationmentioning

confidence: 96%

Computational Studies of Synthetically Relevant Homogeneous Organometallic Catalysis Involving Ni, Pd, Ir, and Rh: An Overview of Commonly Employed DFT Methods and Mechanistic Insights

et al. 2015

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Section: C−h Bond Activationmentioning

confidence: 96%

Computational Studies of Synthetically Relevant Homogeneous Organometallic Catalysis Involving Ni, Pd, Ir, and Rh: An Overview of Commonly Employed DFT Methods and Mechanistic Insights

et al. 2015

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“…A heterobimetallic PdAg(OAc) 3 6 , 37.9 kcal mol −1 ); moreover, for the monomeric and trimeric systems, an ortho selectivity was predicted. Sunoj, Schaefer, and Anand have also considered the role of AgOAc and CsF additives in the Pd(OAc) 2 -catalyzed amination of N-arylbenzamides with N-oxyand N-chloromorpholines [24] (20-21, Figure 1.8) [25]. Using M06(DCE) calculations, a standard acetate-assisted C-H activation of the N-deprotonated substrate has a computed barrier of +28.1 kcal mol −1 .…”

Section: Early Computational Studiesmentioning

confidence: 99%

“…(a) Pd-catalyzed amination of N-arylbenzamides (experiment, R = t Bu, Ar = 4-C 6 F 4 CF 3 , X = Cl, OAc,OBz) and (b) computed CsF-stabilized heterobimetallic transition state (R = Ar = H)[25].…”

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confidence: 99%

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Computational Studies of Heteroatom‐Assisted CH Activation at Ru, Rh, Ir, and Pd as a Basis for Heterocycle Synthesis and Derivatization

Carr¹,

Macgregor²,

McMullin³

2016

Transition Metal‐Catalyzed Heterocycle Synthesis via CH Activation

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IntroductionModern computational chemistry is a key tool by which insight into organometallic reaction mechanisms can be gained. The ability to characterize short-lived intermediates and transition states provides an ideal complement to experiment, where such information is often extremely difficult, if not impossible, to obtain. Recent years have seen great advances in understanding the mechanisms of C-H bond activation, and this area was the subject of several major reviews toward the end of the last decade [1,2]. More recently, the focus has shifted to how C-H activation can be integrated into catalytic cycles for useful organic transformations. The C-H bond activation event is itself mechanistically diverse, with oxidative addition (OA), σ-bond metathesis (SBM), and electrophilic activation (EA) all potentially available at late transition metal centers, depending on the metal, its oxidation state, and the coordination environment. C-H activation assisted by a heteroatom base (typically a carboxylate or carbonate) falls into the last of these categories and forms the focus of this chapter. More recently, computational studies of catalytic cycles for C-H activation and functionalization have become more common. These reveal the complexity of what are usually multiple-step processes, and calculations are particularly well placed to test different mechanistic possibilities. Such studies are most effectively pursued through a close interaction between experiment and computation, and increasingly this is allowing for a more quantitative assessment of computed reaction mechanisms.As well as progress in mechanistic understanding, the last 10 years have seen important developments in the computational methodologies available to model transition metal reactivity. While density functional theory (DFT) remains the core method of choice, the ability to model larger systems that more closely reflect experiment has highlighted the known shortcomings of DFT in describing dispersion interactions. These long-range, stabilizing interactions are individually weak, but their cumulative effect in large systems can be significant. Methods to incorporate this component include its separate calculation (e.g., Transition Metal-Catalyzed Heterocycle Synthesis via C-H Activation, First Edition. Edited by Xiao-Feng Wu.

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“…To our knowledge, a five-coordinate Pd transition structure is unprecedented, and is in vast contrast to the traditional mechanism transition state currently theorised in the literature. [21][22][23] The four-coordinate transition state is favoured in the absence of MeCN (2TS vs. 3TS in ESI), however, these studies indicate that a five-coordinate transition structure may be more general in the presence of strong coordinating solvents. Further, the origin of palladacyclisation was evaluated against competitive bis-NHC complexation.…”

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σ-Alkenyl endo-palladacycle formation via regiospecific functionalisation of an unreactive NHC-tethered C(sp²)–H bond

et al. 2015

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Non-innocent Additives in a Palladium(II)-Catalyzed C–H Bond Activation Reaction: Insights into Multimetallic Active Catalysts

Cited by 122 publications

References 62 publications

Computational Studies of Synthetically Relevant Homogeneous Organometallic Catalysis Involving Ni, Pd, Ir, and Rh: An Overview of Commonly Employed DFT Methods and Mechanistic Insights

Computational Studies of Synthetically Relevant Homogeneous Organometallic Catalysis Involving Ni, Pd, Ir, and Rh: An Overview of Commonly Employed DFT Methods and Mechanistic Insights

Computational Studies of Heteroatom‐Assisted CH Activation at Ru, Rh, Ir, and Pd as a Basis for Heterocycle Synthesis and Derivatization

σ-Alkenyl endo-palladacycle formation via regiospecific functionalisation of an unreactive NHC-tethered C(sp²)–H bond

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Non-innocent Additives in a Palladium(II)-Catalyzed C–H Bond Activation Reaction: Insights into Multimetallic Active Catalysts

Cited by 122 publications

References 62 publications

Computational Studies of Synthetically Relevant Homogeneous Organometallic Catalysis Involving Ni, Pd, Ir, and Rh: An Overview of Commonly Employed DFT Methods and Mechanistic Insights

Computational Studies of Synthetically Relevant Homogeneous Organometallic Catalysis Involving Ni, Pd, Ir, and Rh: An Overview of Commonly Employed DFT Methods and Mechanistic Insights

Computational Studies of Heteroatom‐Assisted CH Activation at Ru, Rh, Ir, and Pd as a Basis for Heterocycle Synthesis and Derivatization

σ-Alkenyl endo-palladacycle formation via regiospecific functionalisation of an unreactive NHC-tethered C(sp2)–H bond

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σ-Alkenyl endo-palladacycle formation via regiospecific functionalisation of an unreactive NHC-tethered C(sp²)–H bond