Mechanistic Studies on the Pd‐catalyzed Direct CH Arylation of 2‐Substituted Thiophene Derivatives with Arylpalladium Bipyridyl Complexes

Steinmetz, Marc; Ueda, Kirika; Grimme, Stefan; Yamaguchi, Junichiro; Kirchberg, Sylvia; Itami, Kenichiro; Studer, Armido

doi:10.1002/asia.201101011

Cited by 62 publications

(36 citation statements)

References 87 publications

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“…Grimme, Itami, Studer, and coworkers used dispersion-corrected DFT (B2PLYP-D3//TPSS-D3) to model the reaction of [Pd(bpy)Ph] + with the parent thiophene and showed that insertion into the Pd-Ph bond had an intrinsic preference for phenyl transfer onto the C4-position [44]. Fu and coworkers considered the reactions of 2-phenyl-3-methoxythiophene at Pd(Ph)(κ 1 -CO 3 H)(bpy) and Pd(Ph)(κ 2 -CO 3 H){P(OR) 3 } (R = OMe, CH(CF 3 ) 2 ) using an M06(toluene)//B3LYP protocol [45].…”

Section: Direct Functionalization Via C-h Activation Of Heterocyclic mentioning

confidence: 99%

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: Direct Functionalization Via C-h Activation Of Heterocyclic mentioning

confidence: 99%

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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“…[14,15,17] This protocol employing 2 b opened a general access to β-(4alchoxyphenyl)thiophenes 27-29. In all cases, the arylation of thiophenes with 2 b completed in shorter reaction time than 2 a and provided products (27)(28)(29) in higher yields than the phenyl analogues 20, 22, and 26, respectively. These results illustrate the effectiveness of the arylantimony reagent as an aryl group donor in challenging cross-coupling reactions.…”

Section: Resultsmentioning

confidence: 89%

Pd‐Catalyzed β‐Selective C−H Arylation of Thiophenes with Triarylantimony Difluorides

et al. 2018

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Regioselective CÀ H arylation using pentavalent organoantimony compounds as a new class of arylating reagents is described. The reaction of thiophenes with triarylantimony difluorides in the presence of 5 mol% of PdðOAcÞ 2 and 2 equiv. CuCl 2 at 80°C under aerobic conditions afforded the β-arylated thiophene derivatives in moderate-to-high yields. The reaction is sensitive to the electronic nature of the triarylantimony difluorides -those bearing an electron-donating group on the phenyl ring showed higher reactivity than those have an electron-withdrawing group. Scheme 1. Arylating reagents (ArÀ X) for Pd-catalyzed β-selective CÀ H arylation of thiophenes.

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“…Considering all these results, the mechanism probably involves activation of the Si−H bond at the particle surface and that the surface bound silyl group then regioselectively inserts into the alkyne in the second step. The surface‐bound metal–alkenyl species is then likely deprotonated by the added base to give the product 3 a . When the reaction was carried out under Ar atmosphere, the transformation was incomplete, and a larger amount of hydrosilylation side‐product and styrene were formed.…”

Section: Methodsmentioning

confidence: 99%

Tuning the Selectivity of AuPd Nanoalloys towards Selective Dehydrogenative Alkyne Silylation

Wissing

Studer

2019

Chemistry A European J

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The cross‐dehydrogenative coupling of terminal alkynes and hydrosilanes catalyzed by AuPd nanoalloys is described. Metal nanoparticles are readily prepared in 15 minutes from commercially available and cheap starting materials by using a photochemical approach. The ratio of Au and Pd in the alloys heavily influences their reactivity. These cooperative nanoalloy catalysts tolerate a large number of functional groups (e.g., free amines and acids), operate at room temperature under air atmosphere at low loading (2 mol %), and the cross‐dehydrogenative coupling can easily be scaled up.

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Mechanistic Studies on the Pd‐catalyzed Direct CH Arylation of 2‐Substituted Thiophene Derivatives with Arylpalladium Bipyridyl Complexes

Cited by 62 publications

References 87 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

Pd‐Catalyzed β‐Selective C−H Arylation of Thiophenes with Triarylantimony Difluorides

Tuning the Selectivity of AuPd Nanoalloys towards Selective Dehydrogenative Alkyne Silylation

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