Controlling the oxidative addition of aryl halides to Au(I)

Fernández, Israel; Wolters, Lando P.; Bickelhaupt, F. Matthias

doi:10.1002/jcc.23734

Cited by 70 publications

(64 citation statements)

References 58 publications

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“…Strain and ligand environment induced oxidativea ddition of Au I complexest ot he CÀCand CÀCO bonds of biphenylene and benzocyclobutenone. [225] The activation strain analysis is au seful toolf or the rational design of Au complexes and reactantst oa chieve facile oxidative additiona nd reductive elimination at Au centers. [223] Scheme34.…”

Section: Oxidant-free Oxidative Addition Of C-heteroatom Bonds To Au mentioning

confidence: 99%

Gold‐Catalyzed Cross‐Coupling Reactions: An Overview of Design Strategies, Mechanistic Studies, and Applications

Nijamudheen

Datta

2019

Chemistry A European J

153

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Transition-metal-catalyzed cross-couplingr eactions are central to many organic synthesis methodologies. Traditionally,P d, Ni, Cu, and Fe catalysts are used to promote these reactions. Recently,m any studies have showedt hat both homogeneous and heterogeneous Au catalysts can be used for activating selective cross-coupling reactions.H ere, an overview of the past studies, current trends, andf uture directions in the field of gold-catalyzed coupling reactions is presented.D esign strategiest oa ccomplish selective homocoupling and cross-coupling reactions under both homogeneous and heterogeneous conditions, computational and ex-perimental mechanistic studies, and their applicationsi nd iverse fields are critically reviewed. Specific topics covered are:o xidant-assisted and oxidant-free reactions;s train-assisted reactions;d ual Au and photoredoxc atalysis;b imetallic synergistic reactions;m echanismso fr eductivee limination processes;e nzyme-mimicking Au chemistry;c lustera nd surface reactions;a nd plasmonic catalysis. In the relevant sections, theoretical and computational studies of Au I /Au III chemistry are discussed and the predictionsf rom the calculationsa re compared with the experimental observations to derive useful design strategies.A. Nijamudheen earnedh is PhD from IACS, Kolkata,i n2 015. Currently,h ei sapostdoctoral researcher atF loridaS tate University.H is researchi nterests are in computational catalysis, solar energym aterials, and beyond Li-ion battery technologies.Ayan Dattai sc urrently aP rofessor at IACS, Kolkata.H is research interests include theoretical and computational studieso ft ransitionmetal-catalyzed reactions,o pto-electronic properties of organic and solid-statem aterials, and the design of renewableenergymaterials. He has won several awards including the DST-SERB Distinguished Investigator Award (DIA) in 2019.

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Section: Oxidant-free Oxidative Addition Of C-heteroatom Bonds To Au mentioning

confidence: 99%

Gold‐Catalyzed Cross‐Coupling Reactions: An Overview of Design Strategies, Mechanistic Studies, and Applications

Nijamudheen

Datta

2019

Chemistry A European J

153

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“…More precisely, in all cases, there is either a slight preference for the formation of the endo adduct (for 1, 2, 5, and 6) or endo and exo adduct have essentially the same barrier (for 3 and 4). [19] Also, the 1,4 and 1,5-transition states for the reaction of MeN 3 with dipolarophiles 1-6 were computed (Table 1, in parenthesis). This is in line with the fact that, in these reactions, the determining group for the stereochemistry is the sterically little-demanding hydrogen atom of the dipole.…”

Section: Trends In Reactivitymentioning

confidence: 99%

“…[3,10] In these cases, different stereoisomers (endo or exo) can be formed, depending on the preferential interactions between the substituent groups in the transition state structure. [19,20] It is therefore desirable to know how the regioand stereochemistry of the formed cycloproducts can be controlled by changing the electronic demand of substituent groups at the dipole or dipolarophile. On the other hand, the presence of electron-withdrawing groups, R = CN or NO 2 , leads to 1,4-addition.…”

Section: Introductionmentioning

confidence: 99%

Regio‐ and Stereoselectivity in 1,3‐Dipolar Cycloadditions: Activation Strain Analyses for Reactions of Hydrazoic Acid with Substituted Alkenes

2017

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We quantum chemically explore and analyze 1,3‐dipolar cycloadditions of hydrazoic acid and methyl azide with a number of substituted alkenes R‐HC=CH2 (R = CH3, OH, OCH3, NH2, CN, and NO2) by using dispersion‐corrected DFT at wB97X‐D/6‐311++G(d,p). Our purpose is to uncover the physical factors behind the computed trends in reactivity, regioselectivity (1,4 vs. 1,5 addition), and preferred stereochemistry (endo vs. exo). To this end, we use the activation strain model (ASM) and quantitative molecular orbital (MO) theory. One of our main findings is that introducing electron‐donating groups in the dipolarophile, R = CH3, OH, OCH3, or NH2, favors the 1,5‐cycloaddition. On the other hand, the presence of electron‐withdrawing groups, R = CN or NO2, leads to 1,4‐addition. Besides, we find a general preference for endo addition, a result that consolidates the endo rule. Trends in the regiochemistry are dictated by the inverse and regular HOMO–LUMO gap, respectively, between dipole and dipolarophile.

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“…Conveniently, there is no special computer code required to perform activation strain analyses: all necessary quantities can be computed using any of the regular quantum‐chemical software packages available. As a result, the activation strain model has been applied by various research groups, on a range of chemical processes, such as nucleophilic substitution, cycloaddition, oxidative addition, isomerization, and many other processes from organic and organometallic chemistry.…”

Section: Introductionmentioning

confidence: 99%

The activation strain model and molecular orbital theory

Wolters

Bickelhaupt

2015

WIREs Comput Mol Sci

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314

229

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The activation strain model is a powerful tool for understanding reactivity, or inertness, of molecular species. This is done by relating the relative energy of a molecular complex along the reaction energy profile to the structural rigidity of the reactants and the strength of their mutual interactions: ΔE(ζ) = ΔEstrain(ζ) + ΔEint(ζ). We provide a detailed discussion of the model, and elaborate on its strong connection with molecular orbital theory. Using these approaches, a causal relationship is revealed between the properties of the reactants and their reactivity, e.g., reaction barriers and plausible reaction mechanisms. This methodology may reveal intriguing parallels between completely different types of chemical transformations. Thus, the activation strain model constitutes a unifying framework that furthers the development of cross-disciplinary concepts throughout various fields of chemistry. We illustrate the activation strain model in action with selected examples from literature. These examples demonstrate how the methodology is applied to different research questions, how results are interpreted, and how insights into one chemical phenomenon can lead to an improved understanding of another, seemingly completely different chemical process. WIREs Comput Mol Sci 2015, 5:324–343. doi: 10.1002/wcms.1221

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Controlling the oxidative addition of aryl halides to Au(I)

Cited by 70 publications

References 58 publications

Gold‐Catalyzed Cross‐Coupling Reactions: An Overview of Design Strategies, Mechanistic Studies, and Applications

Gold‐Catalyzed Cross‐Coupling Reactions: An Overview of Design Strategies, Mechanistic Studies, and Applications

Regio‐ and Stereoselectivity in 1,3‐Dipolar Cycloadditions: Activation Strain Analyses for Reactions of Hydrazoic Acid with Substituted Alkenes

The activation strain model and molecular orbital theory

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