Predictable and Site-Selective Functionalization of Poly(hetero)arene Compounds by Palladium Catalysis

Lapointe, David; Markiewicz, Thomas; Whipp, Christopher J.; Toderian, Amy B.; Fagnou, Keith

doi:10.1021/jo102081a

Cited by 154 publications

(68 citation statements)

References 48 publications

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“…The accelerating effect of electron-withdrawing substituents is again apparent, for example, in the lower barrier for C2-H activation of 3-fluorobenzothiophene compared to benzothiophene. The overall trends in reactivity and the regioselectivities predicted in this paper were subsequently verified experimentally [36].…”

Section: Early Computational Studiessupporting

confidence: 59%

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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Section: Early Computational Studiessupporting

confidence: 59%

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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“…of K 2 CO 3 gave selectively 3-(3-nitrophenyl)-2-(thiophen-2-yl)indolizine-1-carboxylate (309) in 75% yield (Scheme 161). [206] In agreement with the predicted reactivity of the heteroarenes by the DFT-calculated CMD pathway promoted by Pd carboxylate complexes, the thiophene ring of compound 308 proved to be significantly less reactive than the pyrrole ring of such a compound and did not react with the aryl bromide. [206] More recently, You, Lan and co-workers established that methyl indolizine-2-carboxylate (310) was able to react with 2 equiv.…”

Section: P(o)h Was Employed As the Prea C H T U N G T R E N N U N G Lsupporting

confidence: 69%

Cross‐Coupling of Heteroarenes by CH Functionalization: Recent Progress towards Direct Arylation and Heteroarylation Reactions Involving Heteroarenes Containing One Heteroatom

et al. 2014

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In recent years, transition metal-catalyzed direct (hetero)arylation reactions of heteroarenes with (hetero)aryl halides and pseudohalides have received significant attention as eco-friendly and economic alternatives to classical methods for the construction of heteroaryl-(hetero)aryl C À C bonds by transition metal-catalyzed cross-couplings involving the use of stoichiometric amounts of organometallic reagents. This critical review with 430 references covers the results obtained in the period January 2009 to February 2013 in the area of the transition metal-catalyzed direct inter-and intramolecular (hetero)arylation reactions of heteroarenes containing one heteroatom. Particular attention has been given to illustrate chemo-and site selectivity aspects of these reactions as well applications of these C À C bond forming reactions in the synthesis of pharmaceutically relevant compounds, natural products and their analogues and precursors. The most recent advancements into the mechanism(s) of these reactions have also been briefly reported.

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“…Simple thiophene rings are known to be less reactive in C–H functionalization reactions [42]; nevertheless, 11 was successfully arylated in moderate to good yields, depending on the electronic properties of the bromobenzene substituents (Table 4, entries 11–13, 57–90%). Electron rich 4-methoxybromobenzene reacted more efficiently than the electron poor 4-fluorobromobenzene.…”

Section: Resultsmentioning

confidence: 99%

Extending the utility of [Pd(NHC)(cinnamyl)Cl] precatalysts: Direct arylation of heterocycles

Martín¹,

Chartoire²,

Slawin³

et al. 2012

Beilstein J. Org. Chem.

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SummaryThe use of [Pd(NHC)(cinnamyl)Cl] precatalysts in the direct arylation of heterocycles has been investigated. Among four different precatalysts, [Pd(SIPr)(cinnamyl)Cl] proved to be the most efficient promoter of the reaction. The C–H functionalization of sulfur- or nitrogen-containing heterocycles has been achieved at low catalyst loadings. These catalyst charges range from 0.1 to 0.01 mol % palladium.

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Predictable and Site-Selective Functionalization of Poly(hetero)arene Compounds by Palladium Catalysis

Cited by 154 publications

References 48 publications

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

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

Cross‐Coupling of Heteroarenes by CH Functionalization: Recent Progress towards Direct Arylation and Heteroarylation Reactions Involving Heteroarenes Containing One Heteroatom

Extending the utility of [Pd(NHC)(cinnamyl)Cl] precatalysts: Direct arylation of heterocycles

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