Gold-Catalyzed Ring Expansion of Enyne-Lactone: Generation and Transformation of 2-Oxoninonium

Luo, Kun; Cao, Tongxiang; Jiang, Huanfeng; Chen, Lianfen; Zhu, Shifa

doi:10.1021/acs.orglett.7b02834

Cited by 19 publications

(7 citation statements)

References 61 publications

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“…Chen, Zhu, and co-workers demonstrated that by changing the ligands in the gold(I) complex the enyne-lactones 92a can be efficiently transformed to either naphthalene derivatives 92b or benzo-fused polycyclic compounds 92c (Scheme ). , The combination of Ph 3 PAuCl and AgSbF 6 favored the 6- endo - dig cyclization, resulting from the attack of O-nucleophile on the activated alkyne, followed by ring expansion to generate an interesting nine-membered 2-oxo-oxoninium intermediate 92d . It was proposed that the intermediate 92d after a 6π-electrocyclization/aromatization sequence produces various naphthalene derivatives 92b .…”

Section: Ligand-dependent Divergent Gold Catalysis (Ldgc)mentioning

confidence: 99%

Divergent Gold Catalysis: Unlocking Molecular Diversity through Catalyst Control

et al. 2021

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The catalyst-directed divergent synthesis, commonly termed as “divergent catalysis”, has emerged as a promising technique as it allows chartering of structurally distinct products from common substrates simply by modulating the catalyst system. In this regard, gold complexes emerged as powerful catalysts as they offer unique reactivity profiles as compared to various other transition metal catalysts, primarily due to their salient electronic and geometrical features. Owing to the tunable soft π-acidic nature, gold catalysts not only evolved as superior contenders for catalyzing the reactions of alkynes, alkenes, and allenes but also, more intriguingly, have been found to provide divergent reaction pathways over other π-acid catalysts such as Ag, Pt, Pd, Rh, Cu, In, Sc, Hg, Zn, etc. The recent past has witnessed a renaissance in such examples wherein, by choosing gold catalysts over other transition metal catalysts or by fine-tuning the ligands, counteranions or oxidation states of the gold catalyst itself, a complete reactivity switch was observed. However, reviews documenting such examples are sporadic; as a result, most of the reports of this kind remained scattered in the literature, thereby hampering further development of this burgeoning field. By conceptualizing the idea of “Divergent Gold Catalysis (DGC)”, this review aims to consolidate all such reports and provide a unified approach necessary to pave the way for further advancement of this exciting area. Based on the factors governing the divergence in product formation, an explicit classification of DGC has been provided. To gain a fundamental understanding of the divergence in observed reactivities and selectivities, the review is accompanied by mechanistic insights at appropriate places.

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Section: Ligand-dependent Divergent Gold Catalysis (Ldgc)mentioning

confidence: 99%

Divergent Gold Catalysis: Unlocking Molecular Diversity through Catalyst Control

et al. 2021

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“…[47] Sulfonic acids such as HOTf are being used more frequently to promote such reactions, as shown by Zhu's group in a single example. [48] HOTf and MsOH have then been used several times to promote the formation of extended fluorenone in the field of optoelectronics by Frigoli's team [49] and Park's group (Scheme 18). [50] Electrophilic cyclisation has also been described from Ntosyl naphthamides leading to tetra-and pentacyclic fluorenones (Scheme 19).…”

Section: Construction Of Ring a From Ortho Functionalized Biaryl Precursorsmentioning

confidence: 99%

On the Shape and Synthesis of Extended Fluorenones: Recent Advances and Upcoming Challenges

Large

Prim

2021

Eur J Org Chem

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Extended fluorenones represent a particular class of polycyclic compounds. The extension of the aromatic system through the fusion of additional benzene rings onto the central tricyclic fluorenone gives rise to an impressive topological diversity and allows to modulate the properties of the original molecule. The multiple ways this aromatic extension can be joined onto the tricyclic core generates multiple spatial arrangements from linear, angular, mixed linear-angular, to helical. This extensive range of shapes and their subsequent applications has piqued the curiosity of the scientific community, who now creatively compete to develop selective and direct routes to these valuable molecular architectures. Potential applications of these diverse domains have also driven the development of strategies for the installation of various substituents at selected sites of the carbon backbone. This review intends to provide the reader with an up-to-date overview of the methods for constructing extended fluorenones and their properties. Damien Prim studied chemistry at the Paul Verlaine University of Metz, where he received his Ph.D. in organic chemistry in 1994 under the guidance of Prof. Gilbert Kirsch. After a postdoctoral period with Prof. Léon Ghosez at UC Louvain-la-Neuve, Belgium, he was appointed as an assistant professor at Paul Verlaine University of Metz. In 1999, he moved to Pierre et Marie Curie University in Paris as a CNRS research associate. He then moved to the University of Versailles St Quentin as an assistant professor in 2001. In 2005, he was appointed as a full professor of chemistry at the University of Versailles St Quentin. Since 2020, he has been head of the Graduate School of Chemistry at the University of Paris-Saclay. His research focuses on homogeneous and heterogenous catalysis and the syntheses and properties of polycyclic molecular architectures. Benjamin Large studied chemistry at the Ecole Nationale Supérieure de Chimie de Montpellier, France, and then joined Damien Prim's team at the University of Versailles St Quentin as a Ph.D. student. His thesis was focused on the selective C-H functionalization of naphthalene and its derivatives. After obtaining his Ph.D. in 2019, Benjamin joined Anne-Kathrin Duhme-Klair's team as a postdoctoral research associate at the University of York (UK), and is currently working on the development of artificial metalloenzymes

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“…Both intermediates 102a and 102b then undergo an interesting 6π electrocyclization reaction and subsequent aromatization process toward compounds 99 and 101 , respectively. The addition of one equivalent of water is required for the formation of 99 whereas the diester 101 is isolated even in anhydrous media (Figure 10A) (Luo et al, 2017). On the other hand, the nature of the ligand at the gold(I)-catalyst seems to have a high influence in the evolution of the mechanism allowing the transformation of related enyne-lactones 103 .…”

Section: Gold-catalyzed Isomerization Processes Involving An Initimentioning

confidence: 99%

Gold-Catalyzed Homogeneous (Cyclo)Isomerization Reactions

2019

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Gold is currently one of the most used metals in organometallic catalysis. The ability of gold to activate unsaturated groups in different modes, together with its tolerance to a wide range of functional groups and reaction conditions, turns gold-based complexes into efficient and highly sought after catalysts. Natural products and relevant compounds with biological and pharmaceutical activity are often characterized by complex molecular structures. (Cyclo)isomerization reactions are often a useful strategy for the generation of this molecular complexity from synthetically accessible reactants. In this review, we collect the most recent contributions in which gold(I)- and/or gold(III)-catalysts mediate intramolecular (cyclo)isomerization transformations of unsaturated species, which commonly feature allene or alkyne motifs, and organize them depending on the substrate and the reaction type.

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Gold-Catalyzed Ring Expansion of Enyne-Lactone: Generation and Transformation of 2-Oxoninonium

Abstract: An efficient gold-catalyzed ring-expansion reaction of enyne-lactones to form 2-oxoninonium intermediates is reported. The 2-oxoninonium generated in this work could undergo further 6π electrocyclization and aromatization reaction to produce different aromatic compounds.

Cited by 19 publications

References 61 publications

Divergent Gold Catalysis: Unlocking Molecular Diversity through Catalyst Control

Divergent Gold Catalysis: Unlocking Molecular Diversity through Catalyst Control

On the Shape and Synthesis of Extended Fluorenones: Recent Advances and Upcoming Challenges

Gold-Catalyzed Homogeneous (Cyclo)Isomerization Reactions

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