Gold-Catalyzed Post-Ugi Ipso-Cyclization with Switchable Diastereoselectivity

Nechaev, Anton A.; Hecke, Kristof Van; Zaman, Manzoor; Kashtanov, Stepan; Ungur, Liviu; Pereshivko, Olga P.; Peshkov, Vsevolod A.; Eycken, Erik V. Van der

doi:10.1021/acs.joc.8b00953

Cited by 42 publications

(28 citation statements)

References 89 publications

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“…Two diastereomeric dienones were isolated depending on both the gold-catalyst and the reaction conditions. Taking the 140 yields into account and supported by a conformational theoretical analysis, the authors concluded that the isomer 140a resulting from the catalytic treatment with Ph 3 PAuCl is energetically more favorable than that derived from the bulkier JhonPhosAuCl precatalyst ( 140b ) (Nechaev et al, 2018). A related work had been previously published by the same group (He et al, 2017).…”

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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Section: Gold-catalyzed Isomerization Processes Involving An Initimentioning

confidence: 99%

Gold-Catalyzed Homogeneous (Cyclo)Isomerization Reactions

2019

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“…Peshkov, Van der Eycken, and co-workers, in 2018, reported a very unique diastereoselective-switchable transformation of Ugi adducts 93a, obtained from the reaction of alkynoic acid, aldehydes, aminophenols, and isocyanides in methanol. 272 It was demonstrated that when Ugi adducts 93a were subjected to a cationic gold(I) catalyst the ipso-cyclization products such as spirocyclic pyrrol-2-one-dienones 93b and 93c can be efficiently obtained (Scheme 93). More importantly, the diastereoselectivity of these reactions was effectively controlled by varying the electronic and steric properties of ligands, the nature of the counteranion, as well as the solvent, temperature, and catalyst loading.…”

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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“…The same principle, both for the production of the substrates by Ugi MCR and the Au-mediated cycloisomerization was reported by Peshkov and Van der Eycken (Scheme 135, part B). 241 In this case, ortho-amino phenol derivatives 585 were employed thus allowing the formation of spirolactams 586 in which the carbonyl is formed α to the spiro center. Interestingly, two catalytic systems were employed, each allowing the selective formation of one of the two diastereoisomers.…”

Section: Alkynyl Carbonyl Derivativesmentioning

confidence: 99%

“…It was also shown that an Ugi MCR allowed for the rapid synthesis of diverse N -substituted lactams that could be readily cyclodearomatized under gold catalysis (see 584 ). The same principle, both for the production of the substrates by Ugi MCR and the Au-mediated cycloisomerization was reported by Peshkov and Van der Eycken (Scheme , part B) …”

Section: Carbon π-Systems With Electron-withdrawing Groupsmentioning

confidence: 99%

Gold-Catalyzed Reactions of Specially Activated Alkynes, Allenes, and Alkenes

et al. 2020

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This review describes the gold-catalyzed reactions of specially activated alkynes, allenes, and alkenes. Such species are characterized by the presence of either electron-donating or electron-withdrawing groups as substituents of the carbon π-system. They are intrinsically polarized, and when compared to their nonspecially activated counterparts can therefore be involved in gold-catalyzed transformations featuring increased regio-, stereo-, and chemoselectivities. The chemistry of specially activated carbon π-systems under homogeneous gold catalysis is extremely rich and varied. The reactivity observed with nonspecially activated unsaturated systems can often be transposed to specially activated ones without loss of efficiency. However, specially activated carbon π-systems also exhibit specific reactivities that cannot be attained with regular substrates. In this family of carbon π-systems, ynamides and their analogs, along with alkynyl carbonyl derivatives, are the classes of substrates that have retained the most attention. This review provides an overview of the chemistry developed with all classes of specially activated carbon π-systems by discussing their general and specific reactivities, presenting and commenting on their gold-catalyzed transformations as well as their applications.

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Gold-Catalyzed Post-Ugi Ipso-Cyclization with Switchable Diastereoselectivity

Cited by 42 publications

References 89 publications

Gold-Catalyzed Homogeneous (Cyclo)Isomerization Reactions

Gold-Catalyzed Homogeneous (Cyclo)Isomerization Reactions

Divergent Gold Catalysis: Unlocking Molecular Diversity through Catalyst Control

Gold-Catalyzed Reactions of Specially Activated Alkynes, Allenes, and Alkenes

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