De Novo Synthesis of Phenols and Naphthols through Oxidative Cycloaromatization of Dienynes

Rong, Mingguang; Qin, Tianzhu; Liu, Xinrui; Wang, Hongfa; Zi, Weiwei

doi:10.1021/acs.orglett.8b02786

Cited by 23 publications

(15 citation statements)

References 55 publications

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“…Larock et al reported a 6‐ endo ‐ dig cyclization of alkynyl benzyl ketones by treatment with excess iodine monochloride (Scheme b) . Recently, Zi group realized an efficient rhodium‐catalyzed oxidative cyclization of enynes in the construction of 2‐naphthols and phenols with remarkable substrate scope, albeit necessitating an external oxidant (Scheme c) . During our study toward intramolecular α‐arylation reactions, we found that ortho ‐bromobenzyl‐substituted α‐fluoroketones 1 under palladium catalysis resulted in the formation of 2‐naphthols 2 .…”

Section: Methodsmentioning

confidence: 67%

“…However, previously reported methods are mainly limited to accessing 1‐naphthol derivatives. To date, only a handful of examples of the de novo construction of polysubstituted 2‐naphthols have been reported . Larock et al reported a 6‐ endo ‐ dig cyclization of alkynyl benzyl ketones by treatment with excess iodine monochloride (Scheme b) .…”

Section: Methodsmentioning

confidence: 99%

“…To date, only a handful of examples of the de novo construction of polysubstituted 2-naphthols have been reported. [16][17][18] Larock et al reported a 6-endo-dig cyclization of alkynyl benzyl ketones by treatment with excess iodine monochloride (Scheme 2b). [17] Recently, Zi group realized an efficient rhodium-catalyzed oxidative cyclization of enynes in the construction of 2-naphthols and phenols with remarkable substrate scope, albeit necessitating an external oxidant (Scheme 2c).…”

mentioning

confidence: 99%

“…[17] Recently, Zi group realized an efficient rhodium-catalyzed oxidative cyclization of enynes in the construction of 2-naphthols and phenols with remarkable substrate scope, albeit necessitating an external oxidant (Scheme 2c). [18] During our study toward intramolecular α-arylation reactions, [19] we found that ortho-bromobenzyl-substituted α-fluoroketones 1 under palladium catalysis resulted in the formation of 2-naphthols 2. These electron-deficient naphthols are not easily accessed by conventional methods.…”

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confidence: 99%

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Synthesis of Polysubstituted 2‐Naphthols by Palladium‐Catalyzed Intramolecular Arylation/Aromatization Cascade

et al. 2020

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A palladium‐catalyzed intramolecular α‐arylation and defluorinative aromatization strategy for the synthesis of polysubstituted 2‐naphthols is reported. With ortho‐bromobenzyl‐substituted α‐fluoroketones as the substrates and palladium acetate/triphenylphosphine as the catalyst, this method features good functional group tolerance, readily available catalyst and starting materials, and high yields. The applications of the strategy are demonstrated by the synthesis of useful building blocks, such as naphtha[2,3‐b]furan, naphthol AS‐D, and ligands/catalysts.

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Section: Methodsmentioning

confidence: 67%

Section: Methodsmentioning

confidence: 99%

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confidence: 99%

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confidence: 99%

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Synthesis of Polysubstituted 2‐Naphthols by Palladium‐Catalyzed Intramolecular Arylation/Aromatization Cascade

et al. 2020

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“…NaBAr4 F (10 mol%), L2 (10 mol% On the other hand, phenols and naphthols were also assembled by Rh-catalyzed oxidative cycloaromatization of dienynes using pyridine N-oxide as external oxidant (Scheme 17). 26 The proposed mechanism involves the formation of a dienyl-ketene intermediate followed by its 6e - electrocyclization/aromatization. The intermediate ketene could be trapped as the ethyl ester derivative when ethanol was used as solvent.…”

Section: Intramolecular Reactionsmentioning

confidence: 99%

Oxidation of Alkynes via Catalytic Metal-Vinylidenes

2020

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Metal-vinylidenes, generated by treatment of terminal alkynes with transition metals, are very useful intermediates in modern synthetic chemistry as shown by the high number of transformations in which they are involved. When a metal-vinylidene is generated in the presence of an oxidant, its immediate oxidation to a ketene occurs. In this short review, recent synthetic applications of the oxidation of alkynes via ketene intermediates from initially formed metal-vinylidenes are highlighted.1 Introduction2 Oxidation of Metal-Vinylidenes with Internal Oxidants3 Oxidation of Metal-Vinylidenes with External Oxidants4 Conclusions

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Vinylidene Complexes

Iwamoto

Ishii

2022

Encyclopedia of Inorganic and Bioinorganic Chemistry

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The parent vinylidene CCH 2 and its substituted analogs CCRR′ are highly unstable isomers of the corresponding alkyne, HCCH and RCCR′, respectively. However, vinylidene complexes, which can be denoted as MCCRR′ in the mononuclear case, are often more stable than η 2 ‐alkyne complexes, and in fact, the most common preparation method for vinylidene complexes is the direct reaction of alkynes (terminal alkynes in most cases) with coordinatively unsaturated metal complexes, although the relative stability of vinylidene and η 2 ‐alkyne complexes depends on the nature of the metal center. The vinylidene ligand may be viewed as an α,β‐unsaturated type of carbene, and the MCCRR′ backbone may also be regarded as a metallaallene. The vinylidene ligand often exhibits a π‐acidic nature, and its character somewhat resembles Fischer‐type carbenes. As a result, vinylidene complexes are widely seen with middle to late transition metals, most typically groups 6, 7, 8, and 9 metals in relatively low oxidation state (typically 0 to III). Owing to its versatile reactivities, vinylidene complexes work as intermediates in many catalytic and stoichiometric conversions of alkynes. Surface vinylidene species are also considered to take part in heterogeneous catalysis such as Fischer–Tropsch reaction, and multinuclear vinylidene complexes are expected to serve as molecular models for such surface species. This article summarizes bonding and structure, physicochemical properties, synthesis, and reactivities including catalytic applications of vinylidene complexes.

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De Novo Synthesis of Phenols and Naphthols through Oxidative Cycloaromatization of Dienynes

Cited by 23 publications

References 55 publications

Synthesis of Polysubstituted 2‐Naphthols by Palladium‐Catalyzed Intramolecular Arylation/Aromatization Cascade

Synthesis of Polysubstituted 2‐Naphthols by Palladium‐Catalyzed Intramolecular Arylation/Aromatization Cascade

Oxidation of Alkynes via Catalytic Metal-Vinylidenes

Vinylidene Complexes

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