Catalytic Regiodivergent Dearomatization Reaction of Nitrosocarbonyl Intermediates with β-Naphthols

Mallik, Sumitava; Bhajammanavar, Vinod; Mukherjee, Arka Probha; Baidya, Mahiuddin

doi:10.1021/acs.orglett.9b00628

Cited by 10 publications

(4 citation statements)

References 63 publications

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“…In 2019, Baidya’s group reported a regioselective oxidative dearomatization reaction (Scheme 12 ). 19 Interestingly, the reaction of α-unsubstituted β-naphthols and hydroxamic acids delivered α-imino-β-naphthalenones in high yields with N -selectivity in the presence of quinidine catalysts. With the Cu(OTf) 2 /bipyridine as catalyst, α-substituted β-naphthols were successfully transformed into α-aminoxylation products with O -selectivity.…”

Section: Construction Of Carbon–nitrogen/oxygen Double Bond At the α-...mentioning

confidence: 99%

Dearomatization of α-Unsubstituted β-Naphthols

Xu,

Li,

Feng

et al. 2023

Synlett

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This Account summarizes the highly appealing dearomatization reactions of β-naphthols for the synthesis of highly functionalized, three-dimensional structures starting with simple planar aromatic compounds. The reactions are categorized mainly from the viewpoint of the construction of carbon–hydrogen, carbon–carbon, and carbon–hetero bonds (C–N/O, C–Cl, C–F) at the α-position of β-naphthols. The dearomatized products play an important role in organic synthesis and materials science.1 Introduction2 Construction of Carbon–Hydrogen Bonds at the α-Position of β-Naphthols3 Construction of Carbon–Carbon Bonds at the α-Position of β-Naphthols4 Construction of Carbon–Nitrogen/Oxygen Double Bond at the α-Position of β-Naphthols5 Construction of Carbon–Carbon and Carbon–Oxygen Bonds at the α-Position of β-Naphthols6 Construction of Carbon–Halogen Bonds at the α-Position of β-Naphthols7 Conclusion

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Section: Construction Of Carbon–nitrogen/oxygen Double Bond At the α-...mentioning

confidence: 99%

Dearomatization of α-Unsubstituted β-Naphthols

Xu,

Li,

Feng

et al. 2023

Synlett

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“…Over the years, chemists have compiled a reaction compendium consisting of nitrosocarbonyl aldol, [8] Henry, [8l] ene, [9] and diverse types of cycloaddition reactions. [10] With our recent programme on nitrosocarbonyl chemistry, [11] we posited previously unexplored nitrosocarbonyl aldol reaction of deconjugated butyrolactams could be a direct route to make heteroatom-substituted unsaturated γ-lactams (Scheme 1c). However, successful execution of this strategy needs to address few challenges.…”

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confidence: 99%

“…The reaction is also effective with other cinchona alkaloid base such as cinchonidine, delivering 3 a in 82% yield (entry 9). Other tertiary amines such as 3quinuclidinol, DABCO, and triethyl amine were also examined where 3 a was isolated in low yields (entries [10][11][12]. In general, O-selectivity was obtained for all these bases, which can be attributed to the more steric hindrance associated with the N-selective nitrosocarbonyl aldol reaction.…”

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confidence: 99%

Regioselective Nitrosocarbonyl Aldol Reaction of Deconjugated Butyrolactams: Synthesis of γ‐Heterosubstituted α,β‐Unsaturated γ‐Lactams

2021

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The nitrosocarbonyl aldol reaction of deconjugated butyrolactams is developed employing quinidine as organocatalyst. The nitrosocarbonyl species generated in situ from hydroxamic acids react with a variety of deconjugated butyrolactams at room temperature, offering valuable α,β-unsaturated γ-lactams bearing heterosubstituted quaternary carbon center in very high yields. This nitrosocarbonyl aldol reaction is O-selective and proceeds exclusively at the γ-center of deconjugated butyrolactams. The reaction is scalable, accommodates diverse functional groups, and is also effective with azodicarboxylates.γ-Lactams and derivatives thereof, particularly those encompass unsaturation in the ring framework and quaternary carbon center at the γ-position, constitute an important class of heterocycles with eminence in medicinal and pharmaceutical chemistry. [1,2] They represent the core structure of many natural products and biologically significant molecules (Figure 1). [2] They are also widely used as versatile building blocks in organic synthesis towards complex targets. [3] Consequently, devising straightforward strategies to access functionally rich unsaturated γ-lactams remains in the limelight of organic synthesis. [4] In this scenario, among the diverse synthetic endeavours, exploration of nucleophilic reactivity of γ-monosubstituted deconjugated butyrolactams have fetched considerable impetus as they are accessible in diverse substitution patterns from readily available precursors. [5] However, this strategy results in dienolate intermediate which could react with electrophile either through the αor γ-position, leading to a mixture of regioisomeric products (Scheme 1a). Further, such reactivity of deconjugated butyrolactams has majorly been investigated for carbon-carbon bond forming reactions and exploration in carbon-heteroatom bond forming reactions are scarce. In 2017, Mukherjee et al. reported sulfenylation and selenylation of γ-monosubstituted deconjugated butyrolac-[a

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“…Among the various electrophilic reaction partners utilized to incorporate heteroatom functionality into organic molecules, nitrosocarbonyl species have received immense impetus as both the C–O and C–N bonds can be constructed from a single source . With our continuous interest in fleeting nitrosocarbonyl chemistry, we envisioned that previously unexplored aldol reactions of γ-substituted deconjugated butenolides with nitrosocarbonyls would be an adorned route to access heteroatom functionalized butenolides (Scheme b,c). However, materialization of this concept is not straightforward.…”

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Catalyst-Controlled Regioselective Nitrosocarbonyl Aldol Reaction of Deconjugated Butenolides

2020

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An unprecedented regiodivergent nitrosocarbonyl aldol reaction of γ-substituted deconjugated butenolides is described. While Lewis base catalyst quinidine leveraged O-selective nitrosocarbonyl aldol reaction exclusively at the γ-position of deconjugated butenolides to produce γ-aminoxylation products, Lewis acid catalyst Cu(OTf)2 steered the competitive N-selective nitrosocarbonyl aldol reaction at the β-position, resulting in heterodifunctionalized butenolides. Both processes were amenable to a broad range of substrates and scalable, while the latter one represents a rare example of one-pot hetero-β,γ-difunctionalization of butenolide scaffolds.

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Catalytic Regiodivergent Dearomatization Reaction of Nitrosocarbonyl Intermediates with β-Naphthols

Cited by 10 publications

References 63 publications

Dearomatization of α-Unsubstituted β-Naphthols

Dearomatization of α-Unsubstituted β-Naphthols

Regioselective Nitrosocarbonyl Aldol Reaction of Deconjugated Butyrolactams: Synthesis of γ‐Heterosubstituted α,β‐Unsaturated γ‐Lactams

Catalyst-Controlled Regioselective Nitrosocarbonyl Aldol Reaction of Deconjugated Butenolides

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