Rapid Assembly of Spironaphthalenones by Dearomative Spiroannulation of Naphthols and Dielectrophiles

Zhao, Dongwei; Liu, Mengtian; Bai, Lu; Liu, Jingjing; Luan, Xinjun

doi:10.1021/acs.joc.3c02067

Cited by 3 publications

(1 citation statement)

References 61 publications

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“…The long-standing synthetic challenge mainly lies not only in the significant ease of rearomatization through proton transfer, but also in the chemoselectivity issue over nucleophilic oxygen or carbon sites, as well as the enantiocontrol . Our strategy proposed to break the current limitation is depicted in Scheme b by recruiting 1-naphthols as bisnucleophiles to undergo a well-organized addition-annulation cascade with designed soft dielectrophiles.…”

Section: Introductionmentioning

confidence: 99%

Asymmetric Dearomatization of Nonfunctionalized 1-Naphthols via Copper-Catalyzed Enantioselective [4 + 1] Spiroannulation

Li,

Guo,

Zhang

et al. 2024

ACS Catal.

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Catalytic asymmetric dearomatization (CADA) is a powerful tool for the rapid construction of complex chiral three-dimensional cyclic molecules featuring quaternary carbon centers from readily available arenes. However, the asymmetric dearomatization of ubiquitous nonfunctionalized 1-naphthols to afford chiral quaternary centers remains challenging and undeveloped. This study reports the asymmetric dearomative [4 + 1] spiroannulation of nonfunctionalized 1-naphthols via copper catalysis. This reaction features a highly chemo-, regio-, and stereoselective nucleophilic addition and intramolecular annulation cascade of a reactive π-extended copper-allenylidene, thus enabling the practical synthesis of a range of valuable spirocyclic enones bearing a chiral quaternary stereocenter with high efficiency. Furthermore, this protocol is applicable to phenols. Control experiments supported the substitution-annulation cascade mechanism by excluding a process involving a 1,3-sigmatropic shift. Preliminary biological activity studies indicated that the synthesized spirocyclic enones hold significant promise as anticancer agents by inducing tumor cell apoptosis.

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Section: Introductionmentioning

confidence: 99%

Asymmetric Dearomatization of Nonfunctionalized 1-Naphthols via Copper-Catalyzed Enantioselective [4 + 1] Spiroannulation

Li,

Guo,

Zhang

et al. 2024

ACS Catal.

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Divergent Synthesis of Naphthalenone Spiroindanediones or 4‐Acyl‐1‐naphthols from Aryl Enaminones Featuring Reuse of Dimethylamine

Yang,

Li,

Zhang

et al. 2024

Adv Synth Catal

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Presented herein is a switchable synthesis of naphthalenone spiroindanediones or 4‐acyl‐1‐naphthols via condition‐controlled divergent cascade reactions of aryl enaminones with diazoindanediones. When the reaction was carried out in the presence of an oxidative additive, naphthalenone spiroindanedione was formed through C(sp2)–H alkylation followed by simultaneous spiroannulation and elimination of dimethylamine. When the reaction was carried out in the presence of an acid additive, on the other hand, 4‐acyl‐1‐naphthol was formed through ring opening of the spiroindanedione moiety attacked by the in situ released dimethylamine. In addition, the reactions are suitable for gram‐scale applications and compatible with a variety of substrates. Moreover, the naphthol products allow structural elaborations and hybridization with clinic drug, thus further enhancing the value of this developed method.

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Base Induced Synthesis of Isochroman Spiropyrazolones Via Bifunctional Peroxides

Feng,

Wang,

2024

Asian J Org Chem

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Isochroman is one of the powerful scaffolds which demonstrated various important biologically activities. Herein we represented the novel and versatile method for the synthesis of valuable isochroman spiropyrazolones of difunctional peroxides and pyrazolones via [1+5] annulation. This process represents a novel spiroisochroman synthesis protocol and is featured by good functional group compatibility, mild conditions and readily available substrates.

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Rapid Assembly of Spironaphthalenones by Dearomative Spiroannulation of Naphthols and Dielectrophiles

Cited by 3 publications

References 61 publications

Asymmetric Dearomatization of Nonfunctionalized 1-Naphthols via Copper-Catalyzed Enantioselective [4 + 1] Spiroannulation

Asymmetric Dearomatization of Nonfunctionalized 1-Naphthols via Copper-Catalyzed Enantioselective [4 + 1] Spiroannulation

Divergent Synthesis of Naphthalenone Spiroindanediones or 4‐Acyl‐1‐naphthols from Aryl Enaminones Featuring Reuse of Dimethylamine

Base Induced Synthesis of Isochroman Spiropyrazolones Via Bifunctional Peroxides

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