Synthesis of 1,2-naphthalenediol derivatives by Rh-catalyzed intermolecular O H insertion reaction of 1,2-diazonaphthoquinones with water and alcohols

Kitamura, Masaya; Otsuka, Kota; Takahashi, Shuhei; Okauchi, Tatsuo

doi:10.1016/j.tetlet.2017.07.084

Cited by 16 publications

(14 citation statements)

References 32 publications

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“…1 H NMR (400 MHz, CDCl 3 ): δ = 7.95 (d, J = 8.4 Hz, 1H), 7.79 (d, J = 8.2 Hz, 1H), 7.57 (d, J = 8.8 Hz, 1H), 7.50 (ddd, J = 8.2, 6.8, 1.2 Hz, 1H), 7.35 (ddd, J = 8.1, 6.8, 1.2 Hz, 1H), 7.23 (d, J = 8.8 Hz, 1H), 5.80 (s, 1H), 3.98 (s, 3H) ppm. 13 C NMR (100 MHz, CDCl 3 ): δ = 145.5, 139.7, 129.7, 128.5, 128.0, 126.5, 125.4, 123.7, 120.4, 117.6, 61.8 ppm …”

Section: Experimental Sectionmentioning

confidence: 99%

Tuning the Reactivity of Peroxo Anhydrides for Aromatic C–H Bond Oxidation

et al. 2018

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Phenol moieties are key structural motifs in many areas of chemical research from polymers to pharmaceuticals. Herein, we report on the design and use of a structurally demanding cyclic peroxide (spiro[bicyclo[2.2.1]heptane-2,4'-[1,2]dioxolane]-3',5'-dione, P4) for the direct hydroxylation of aromatic substrates. The new peroxide benefits from high thermal stability and can be synthesized from readily available starting materials. The aromatic C-H oxidation using P4 exhibits generally good yields (up to 96%) and appreciable regioselectivities.

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Section: Experimental Sectionmentioning

confidence: 99%

Tuning the Reactivity of Peroxo Anhydrides for Aromatic C–H Bond Oxidation

et al. 2018

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“…Diazo quinones (also called quinone diazides) have attracted increasing attention due to their intriguing electronic and structural properties. [1][2][3][4][5] This class of compounds features ap lanar six-membered ring system with diazo, carbonyl and alkene groups in conjugation. [1] This feature makes diazo quinones prone to aromatization to phenols, [2][3][4][5] which are useful synthetic building blocks prevalent in natural products, [6] and endows them with reactivity similar to acceptor/acceptor diazocarbonyl compounds.…”

Section: Introductionmentioning

confidence: 99%

“…[1][2][3][4][5] This class of compounds features ap lanar six-membered ring system with diazo, carbonyl and alkene groups in conjugation. [1] This feature makes diazo quinones prone to aromatization to phenols, [2][3][4][5] which are useful synthetic building blocks prevalent in natural products, [6] and endows them with reactivity similar to acceptor/acceptor diazocarbonyl compounds. [2a,e,4] While diazo quinones are an effective carbene source in av ariety of transition-metal-catalyzed organic transformations, [2][3][4][5] as exemplified by Baranswork on Rh-catalyzed alkene functionalization with diazo quinones, [4] their application in CÀCbond formation under transition-metal-free conditions remains limited.…”

Section: Introductionmentioning

confidence: 99%

Transition‐Metal‐Free C(sp²)–C(sp²) Cross‐Coupling of Diazo Quinones with Catechol Boronic Esters

Zhou

et al. 2020

Angewandte Chemie

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A transition‐metal‐free C(sp2)−C(sp2) bond formation reaction by the cross‐coupling of diazo quinones with catechol boronic esters was developed. With this protocol, a variety of biaryls and alkenyl phenols were obtained in good to high yields under mild conditions. The reaction tolerates various functionalities and is applicable to the derivatization of pharmaceuticals and natural products. The synthetic utility of the method was demonstrated by the short synthesis of multi‐substituted triphenylenes and three bioactive natural products, honokiol, moracin M, and stemofuran A. Mechanistic studies and density functional theory (DFT) calculations revealed that the reaction involves attack of the boronic ester by a singlet quinone carbene followed by a 1,2‐rearrangement through a stepwise mechanism.

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“…Conjugated carbenes based on a carbocyclic backbone have been attracting increasing attention in metal-catalyzed carbene transfer reactions. Notable examples include Rh-catalyzed alkene cyclopropanation recently reported by Baran and co-worker as well as a variety of catalytic processes using diazo quinones (also called quinone diazides), − the key intermediates in which are generally proposed to be metal complexes of the corresponding carbene, herein called quinoid carbene (QC). These proposed M–QC species in the catalytic processes were assumed to undergo QC transfer to various organic targets including C–H bond, alkene, , O–H bond, , anhydride, enol ether, cyclic ether, and halide (Figure a).…”

Section: Introductionmentioning

confidence: 99%

Ruthenium(II) Porphyrin Quinoid Carbene Complexes: Synthesis, Crystal Structure, and Reactivity toward Carbene Transfer and Hydrogen Atom Transfer Reactions

Wang

Wan

et al. 2019

J. Am. Chem. Soc.

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Reactivity study of novel metal carbene complexes can offer new opportunities in catalytic carbene transfer reactions as well as in other synthetic protocols. Metal complexes with quinoid carbene (QC) ligands are assumed to be key intermediates in a variety of metal-catalyzed QC transfer reactions using diazo quinones, which demands development of the chemistry of QC transfer of well characterized metal–QC complexes. Herein we report the isolation and QC transfer of ruthenium porphyrins [Ru(Por)(QC)] which contribute the first examples of (i) structurally characterized metal–QC complex (by X-ray crystallography) and (ii) isolated metal–QC complex that undergoes QC transfer reaction. The complexes [Ru(Por)(QC)] were prepared from reaction of [Ru(Por)(CO)] with diazo quinones and exhibited dual reactivity, i.e., hydrogen atom transfer (HAT) as well as QC transfer. The stoichiometric QC transfer reactions from these Ru–QC complexes to nitrosoarenes (ArNO) afforded nitrones in up to 90% yield, and the corresponding catalytic reactions were also developed. Both the stoichiometric and catalytic reactions for a series of QC ligands bearing electron-donating and -withdrawing substituents showed a reverse substituent effect on the QC transfer reactivity. Complexes [Ru(Por)(QC)] are also reactive toward C–H and X–H (X = N, S) bonds and can catalyze aerobic oxidation of 1,4-cyclohexadiene; their stoichiometric HAT reactions with unsaturated hydrocarbons gave product yields of up to 88%. The unique dual reactivity and electronic feature of [Ru(Por)(QC)] were studied by spectroscopic means and density functional theory (DFT) calculations.

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Synthesis of 1,2-naphthalenediol derivatives by Rh-catalyzed intermolecular O H insertion reaction of 1,2-diazonaphthoquinones with water and alcohols

Cited by 16 publications

References 32 publications

Tuning the Reactivity of Peroxo Anhydrides for Aromatic C–H Bond Oxidation

Tuning the Reactivity of Peroxo Anhydrides for Aromatic C–H Bond Oxidation

Transition‐Metal‐Free C(sp²)–C(sp²) Cross‐Coupling of Diazo Quinones with Catechol Boronic Esters

Ruthenium(II) Porphyrin Quinoid Carbene Complexes: Synthesis, Crystal Structure, and Reactivity toward Carbene Transfer and Hydrogen Atom Transfer Reactions

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Synthesis of 1,2-naphthalenediol derivatives by Rh-catalyzed intermolecular O H insertion reaction of 1,2-diazonaphthoquinones with water and alcohols

Cited by 16 publications

References 32 publications

Tuning the Reactivity of Peroxo Anhydrides for Aromatic C–H Bond Oxidation

Tuning the Reactivity of Peroxo Anhydrides for Aromatic C–H Bond Oxidation

Transition‐Metal‐Free C(sp2)–C(sp2) Cross‐Coupling of Diazo Quinones with Catechol Boronic Esters

Ruthenium(II) Porphyrin Quinoid Carbene Complexes: Synthesis, Crystal Structure, and Reactivity toward Carbene Transfer and Hydrogen Atom Transfer Reactions

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Transition‐Metal‐Free C(sp²)–C(sp²) Cross‐Coupling of Diazo Quinones with Catechol Boronic Esters