Probing the Origin of Challenge of Realizing Metallaphosphabenzenes: Unfavorable 1,2-Migration in Metallapyridines Becomes Feasible in Metallaphosphabenzenes

Wu, Jingjing; Hao, Yulei; Zhu, Jun

doi:10.1038/srep28543

Cited by 8 publications

(3 citation statements)

References 62 publications

(77 reference statements)

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“…For instance, with the aid of computational studies, Jia and co-workers successfully isolated the first rhenabenzenes by introducing alkoxy groups to the rhenabenzene ring . Calculations have suggested that certain palladiabenzenes and rhodiabenzenes might be isolable, η 5 metal indenyl and metal fluorenyl complexes could be applied as starting materials for the synthesis of metallanaphthalenes and metallaanthracenes, respectively, , and some metallaphosphabenzenes might be stable and prepared from half-phosphametallocene. − Unfortunately, these predictions remain to be confirmed experimentally. In addition, reaction mechanism studies rely more and more on computational methods.…”

Section: Conclusion and Outlookmentioning

confidence: 99%

Metallaaromatic Chemistry: History and Development

2020

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Since the prediction of the existence of metallabenzenes in 1979, metallaaromatic chemistry has developed rapidly, due to its importance in both experimental and theoretical fields. Now six major types of metallaromatic compounds, metallabenzenes, metallabenzynes, heterometallaaromatics, dianion metalloles, metallapentalenes and metallapentalynes (also termed carbolongs), and spiro metalloles, have been reported and extensively studied. Their parent organic analogues may be aromatic, non-aromatic, or even anti-aromatic. These unique systems not only enrich the large family of aromatics, but they also broaden our understanding and extend the concept of aromaticity. This review provides a comprehensive overview of metallaaromatic chemistry. We have focused on not only the six major classes of metallaaromatics, including the main-group-metal-based metallaaromatics, but also other types, such as metallacyclobutadienes and metallacyclopropenes. The structures, synthetic methods, and reactivities are described, their applications are covered, and the challenges and future prospects of the area are discussed. The criteria commonly used to judge the aromaticity of metallaaromatics are presented.

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Section: Conclusion and Outlookmentioning

confidence: 99%

Metallaaromatic Chemistry: History and Development

2020

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“…Metallaphosphabenzenes have not yet been realized experimentally. However, their stability and a possible synthetic route have recently been investigated computationally and this may prove to be a fruitful avenue of research in the future.…”

Section: Heterometallabenzenesmentioning

confidence: 99%

Recent Advances in Metallaaromatic Chemistry

Frogley

Wright

2017

Chemistry A European J

142

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Metallaaromatics can be broadly defined as aromatic compounds in which one of the ring atoms is a transition metal. The metallabenzenes are one important class of these compounds that has undergone extensive study recently. Closely related species such as fused-ring metallabenzenes, heterometallabenzenes, π-coordinated metallabenzenes and metallabenzynes have also attracted considerable attention. Although many metallaaromatics can be considered as metalla-analogues of classic organic aromatic compounds, this is not always the case. Recent seminal studies have shown that metallapentalenes and metallapentalynes, which are metalla-analogues of the anti-aromatic compounds pentalene and pentalyne, are in fact aromatic and highly stable. Very unusual spiro-metallaaromatic compounds have also recently been isolated. In this concepts article, key features of all these intriguing metallaaromatic compounds are discussed with reference to the structural, spectroscopic, reactivity and theoretical studies that have been undertaken. These compounds continue to generate much interest, not only because of the contributions they make to fundamental chemical understanding, but also because of the promise of possible practical applications.

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“…Besides, our interest in NHC-catalyzed reactions also prompts us to investigate the origin of selectivities for the competing reactions in detail19202122232425262728293031. In the present study, the commonly used DFT theoretical investigation3233343536373839404142 on the reaction between R1 (in which Ar 1 = para chlorphenyl) and R2 (in which Ar 2 = phenyl) catalyzed by NHC depicted in Fig. 1, was pursued in order to shed light on details of each elementary step at the molecular level and to reach more comprehensive understanding to the enantioselectivity of this interesting reaction.…”

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confidence: 93%

Insights into the Competing Mechanisms and Origin of Enantioselectivity for N-Heterocyclic Carbene-Catalyzed Reaction of Aldehyde with Enamide

Qiao

Chen

Wei

et al. 2016

Sci Rep

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Hydroacylation reactions and aza-benzoin reactions have attracted considerable attention from experimental chemists. Recently, Wang et al. reported an interesting reaction of N-heterocyclic carbene (NHC)-catalyzed addition of aldehyde to enamide, in which both hydroacylation and aza-benzoin reactions may be involved. Thus, understanding the competing relationship between them is of great interest. Now, density functional theory (DFT) investigation was performed to elucidate this issue. Our results reveal that enamide can tautomerize to its imine isomer with the assistance of HCO3−. The addition of NHC to aldehydes formed Breslow intermediate, which can go through cross-coupling with enamide via hydroacylation reaction or its imine isomer via aza-benzoin reaction. The aza-benzoin reaction requires relatively lower free energy barrier than the hydroacylation reaction. The more polar characteristic of C=N group in the imine isomers, and the more advantageous stereoelectronic effect in the carbon-carbon bond forming transition states in aza-benzoin pathway were identified to determine that the imine isomer can react with the Breslow intermediate more easily. Furthermore, the origin of enantioselectivities for the reaction was explored and reasonably explained by structural analyses on key transition states. The work should provide valuable insights for rational design of switchable NHC-catalyzed hydroacylation and aza-benzoin reactions with high stereoselectivity.

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Probing the Origin of Challenge of Realizing Metallaphosphabenzenes: Unfavorable 1,2-Migration in Metallapyridines Becomes Feasible in Metallaphosphabenzenes

Cited by 8 publications

References 62 publications

Metallaaromatic Chemistry: History and Development

Metallaaromatic Chemistry: History and Development

Recent Advances in Metallaaromatic Chemistry

Insights into the Competing Mechanisms and Origin of Enantioselectivity for N-Heterocyclic Carbene-Catalyzed Reaction of Aldehyde with Enamide

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