Selective Synthesis of Six‐Membered and Five‐Membered Spiro Compounds by Controlling the Molar Ratio of Ternary Gallium/Indium/Copper (Ga/In/Cu) Catalysts

Pang, Tao; Sun, Yongjun; Xue, Weijian; Zhu, Yanping; Yu, Guang‐Ao; Wu, Anxin

doi:10.1002/adsc.201201049

Cited by 6 publications

(5 citation statements)

References 32 publications

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“…Earlier use of NMMO [40,41] targeted the extended lifetime of transient o ‐QM through a dipole‐dipole stabilization. However, some o ‐QMs have been formed without the need of NMMO [3,42,43] …”

Section: Resultsmentioning

confidence: 99%

“…However, some o-QMs have been formed without the need of NMMO. [3,42,43] The intramolecular H bond (IMHB)-driven pseudo ring conformation in oxime 2 (with a contribution from nonaromatic strained keto tautomer 2') triggers a redox relay by proton shuttling [Hydrogen AtomTransfer (HAT) or Proton Coupled Electron Transfer (PCET)] [44][45][46][47] at the oxime and phenol OH sites (Scheme 5). This IMHB steers a metal coordination binding mode (Scheme 4, 7 or 7').…”

Section: Chempluschemmentioning

confidence: 99%

See 1 more Smart Citation

Self Cycloaddition of o‐Naphthoquinone Nitrosomethide to (±) Spiro{naphthalene(naphthopyranofurazan)}‐one Oxide: An Insight into its Formation

et al. 2022

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2-Hydroxy-1-naphthaldehyde oxime was oxidized by AgO (or Ag 2 O), in presence of N-methyl morpholine N-oxide (NMMO), to the title spiro adduct-dimer (�)-Spiro{naphthalene-1(2H),4'-(naphtho[2',1':2,3]pyrano[4,5-c]furazan)}-2-one-11'-oxide by a Diels-Alder(DÀ A) type self-cycloaddition, through the agency of an o-naphthoquinone nitrosomethide (o-NQM). Moreover, 2hydroxy-8-methoxy-1-naphthaldehyde oxime was prepared and subjected to the same oxidation conditions. Its sterically guided result, 9-methoxynaphtho[1,2-d]isoxazole, was isolated, instead of the expected spiro adduct. The peri intramolecular H bonding in the oxime is considered to have a key contribution to the outcome. Geometry and energy features of the oxidant-and stereo-guided selectivity of both oxidation outcomes have been explored by DFT, perturbation theory and coupled cluster calculations. The reaction free energy of the DÀ A intermolecular cycloaddition is calculated at À 82.0 kcal/mol, indicating its predominance over the intramolecular cyclization of ca. À 37.6 kcal/mol. The cycloaddition is facilitated by NMMO through dipolar interactions and hydrogen bonding with both metal complexes and o-NQM. The 8(peri)-OMe substitution of the reactant oxime sterically impedes formation of the spiro adduct, instead it undergoes a more facile cyclodehydration to the isoxazole structure by ca. 4.9 kcal/mol.

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Section: Resultsmentioning

confidence: 99%

Section: Chempluschemmentioning

confidence: 99%

Self Cycloaddition of o‐Naphthoquinone Nitrosomethide to (±) Spiro{naphthalene(naphthopyranofurazan)}‐one Oxide: An Insight into its Formation

et al. 2022

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“…9 The Wu group developed a method for the selective synthesis of six-membered and five-membered spironaphthalenones from α-unsubstituted β-naphthols by controlling the molar ratio of ternary gallium/indium/copper (Ga/In/Cu) catalysts (Scheme 1c). 10 The Katsuki group established an iron-salen-catalyzed method for the asymmetric synthesis of spirocyclic (2 H )-dihydrobenzofurans from 1-methyl-2-naphthols and phenols (Scheme 1d). 11 These reports are elegant and inspiring; however, limitations still exist, such as a limited substrate scope and requirement of high loadings of catalysts and other metal reagents.…”

Section: Introductionmentioning

confidence: 99%

Cu(ii)-catalyzed domino construction of spironaphthalenones by dearomatization of β-naphthols and using N,N-dimethylaminoethanol as a C1 synthon

et al. 2023

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“…In 2013, Wu's group proposed a synthesis protocol employing naphthols as starting materials, which successfully delivered the corresponding six-and five-membered spironaphthalenones selectively by controlling the molar ratio of ternary metal catalysts GaCl 3 /InCl 3 /CuCl (Scheme 14). 24 This reaction gives a mild synthetic method for the construction of spironaphthone analogues.…”

Section: Account Synlett 5 Construction Of Carbon-carbon and Carbon-o...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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Selective Synthesis of Six‐Membered and Five‐Membered Spiro Compounds by Controlling the Molar Ratio of Ternary Gallium/Indium/Copper (Ga/In/Cu) Catalysts

Cited by 6 publications

References 32 publications

Self Cycloaddition of o‐Naphthoquinone Nitrosomethide to (±) Spiro{naphthalene(naphthopyranofurazan)}‐one Oxide: An Insight into its Formation

Self Cycloaddition of o‐Naphthoquinone Nitrosomethide to (±) Spiro{naphthalene(naphthopyranofurazan)}‐one Oxide: An Insight into its Formation

Cu(ii)-catalyzed domino construction of spironaphthalenones by dearomatization of β-naphthols and using N,N-dimethylaminoethanol as a C1 synthon

Dearomatization of α-Unsubstituted β-Naphthols

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