Palladium‐Catalyzed Direct CH Functionalization of Benzoquinone

Walker, Sarah E.; Jordan‐Hore, James A.; Johnson, David G.; Macgregor, Stuart A.; Lee, Ai‐Lan

doi:10.1002/ange.201408054

Cited by 14 publications

(3 citation statements)

References 36 publications

(18 reference statements)

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“…Previous literature studies showed that the oxidative Heck reaction, when attempted in water, it led to exclusive formation of the biaryl product via a homocoupling reaction of the arylboronic acids 18a–c. Recently, Macgregor, Lee and co‐workers reported that oxidative Heck coupling can be performed in water medium 18d. Herein we report an oxidative Heck reaction using an abnormal NHC‐coordinated palladium(II) dimer as a catalyst.…”

Section: Introductionmentioning

confidence: 91%

An Abnormal N‐Heterocyclic Carbene‐Based Palladium Dimer: Aqueous Oxidative Heck Coupling Under Ambient Temperature

et al. 2015

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Hereinw er eport the synthesis of an ew abnormal N-heterocyclic carbene( aNHC)-based ligand and its use in synthesizing an acetate bridged C À Ha ctivated palladium dimer (1). In complex 1, the carbenel igand displays an abnormal mode of binding with the palladium(II) ion. We used complex 1 as ac atalyst for the oxidative Heck coupling reac-tion of arylboronic acids with electron-deficient as well as electron-rich olefins at ambient temperature in water to produce selectively the b-arylated products in good to excellent yields. Synthesis of Complex 1Undera na rgon atmosphere,a5 0-mL Schlenk flask was charged with Pd(OAc) 2 (224 mg, 1mmol), L 1 HI (438 mg, 1mmol), and 1,4-dioxane( 15 mL). Ther eaction mixture was heated to 80 8 8Cf or 8h.A fter cooling to room temperature,a ll volatiles were removed under reduced pressure from the reaction mixture.C omplex 1 was obtained by recrystallization from CH 2 Cl 2 /hexane as yellow crystals;y ield: 571 mg (0.6 mmol, 60%);m p2 98-303 8 8C. 1 HNMR (400 MHz, CDCl 3, 25 8 8C, TMS): d = 7.67 (t, J = 7.6 Hz, 1H), Scheme 5. Chemoselectivity study with catalyst 1.

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Section: Introductionmentioning

confidence: 91%

An Abnormal N‐Heterocyclic Carbene‐Based Palladium Dimer: Aqueous Oxidative Heck Coupling Under Ambient Temperature

et al. 2015

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“…Later, Wang and co‐workers introduced a direct disulfide‐directed C─H activation for the synthesis of thiophenols from disulfide and arylboronic acid with oxygen as the oxidant . However, none of the previous methods for 2‐(phenylthio)phenol derivatives synthesis could achieve recycling of the catalyst . From the perspectives of sustainable development and easy recovery, it is clearly necessary to develop a recoverable catalytic system to realize the synthesis of 2‐(phenylthio)phenol derivatives with good efficiency and recyclability.…”

Section: Introductionmentioning

confidence: 99%

“…32 However, none of the previous methods for 2-(phenylthio)phenol derivatives synthesis could achieve recycling of the catalyst. [33][34][35][36][37][38][39][40][41][42][43][44][45][46][47] From the perspectives of sustainable development and easy recovery, it is clearly necessary to develop a recoverable catalytic system to realize the synthesis of 2-(phenylthio)phenol derivatives with good efficiency and recyclability. Based on our continuing efforts towards sustainable development in dehydrogenation, [48][49][50][51][52][53][54] borrowing hydrogen reactions [55][56][57][58][59] and quinone synthesis, [60][61][62][63][64][65][66] herein, we report that the heterogeneous [Cu(binap)I] 2 complex supported on hydrotalcite can be applied to cascade C─H functionalization with sequential hydroxylation from arylboric acids and thiophenols under mild conditions, leading to 2-sulfanylphenols and arylthioquinones, respectively (Fig.…”

Section: Introductionmentioning

confidence: 99%

The Cascade C─H functionalization with sequential hydroxylation and oxidation through heterogeneous BINAP‐copper on hydrotalcite

Zhang

Wang

et al. 2020

J of Chemical Tech & Biotech

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BACKGROUND Aromatic thioether derivatives exist widely in natural products and have significant applications in modern synthesis and the pharmaceutical industry; for example, 2‐sulfanylphenols and arylthioquinones are important intermediates in the processing of anticancer, antibiotic, antivirus and antimalarial drugs. Direct C─H hydroxylation was considered as one of the efficient methods for the synthesis of these compounds. Homogeneous transition metal catalysts usually were used through a cross‐coupling of halogen‐substituted phenols with thiophenols. However, from the perspectives of sustainable development and easy recovery, it is necessary to develop an efficient and recoverable catalytic system to realize the synthesis of aromatic thioether derivatives with good efficiency and recyclability. RESULTS The heterogeneous catalyst [Cu(binap)I]2@HT in the present work showed good catalytic activity for the C─H hydroxylation of benzenethiol and phenylboronic acid. The catalytic system was tolerant to various substituents including alkyl, alkoxy, ester, halogen or trifluoromethyl on the phenyl ring of the thiophenols or arylboric acids. In addition to electron‐donating groups, the products with strong electron‐withdrawing groups, such as methyl formylate and trifluoromethyl also were achieved with good yields at 90 °C for 12 h (68% and 66%, respectively). Repeated experiment results showed that the catalyst could be reused at least five times without obvious decrease in catalytic activity. CONCLUSION A BINAP‐Cu complex supported on hydrotalcite was prepared and used as a heterogeneous catalyst for the C─H activation of thiophenol under mild reaction conditions. Through a cascade C─H hydroxylation and further oxidation process, 2‐Sulfanylphenols and arylthioquinones could be obtained with moderate‐to‐good yields for a series of 2‐(phenylthio)phenol derivatives using the heterogeneous catalyst [Cu(binap)I]2@HT. In addition, this heterogeneous catalyst showed good recylbility. © 2020 Society of Chemical Industry

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Copper‐Catalyzed C(sp²)–C(sp³) Cross‐Dehydrogenative Coupling of Quinones with Cyclic Alkanes: One‐Step Access to Parvaquone and its Analogs

Baral

Kim²,

Lee

2016

Asian J Org Chem

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Palladium‐Catalyzed Direct CH Functionalization of Benzoquinone

Cited by 14 publications

References 36 publications

An Abnormal N‐Heterocyclic Carbene‐Based Palladium Dimer: Aqueous Oxidative Heck Coupling Under Ambient Temperature

An Abnormal N‐Heterocyclic Carbene‐Based Palladium Dimer: Aqueous Oxidative Heck Coupling Under Ambient Temperature

The Cascade C─H functionalization with sequential hydroxylation and oxidation through heterogeneous BINAP‐copper on hydrotalcite

Copper‐Catalyzed C(sp²)–C(sp³) Cross‐Dehydrogenative Coupling of Quinones with Cyclic Alkanes: One‐Step Access to Parvaquone and its Analogs

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Palladium‐Catalyzed Direct CH Functionalization of Benzoquinone

Cited by 14 publications

References 36 publications

An Abnormal N‐Heterocyclic Carbene‐Based Palladium Dimer: Aqueous Oxidative Heck Coupling Under Ambient Temperature

An Abnormal N‐Heterocyclic Carbene‐Based Palladium Dimer: Aqueous Oxidative Heck Coupling Under Ambient Temperature

The Cascade C─H functionalization with sequential hydroxylation and oxidation through heterogeneous BINAP‐copper on hydrotalcite

Copper‐Catalyzed C(sp2)–C(sp3) Cross‐Dehydrogenative Coupling of Quinones with Cyclic Alkanes: One‐Step Access to Parvaquone and its Analogs

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Copper‐Catalyzed C(sp²)–C(sp³) Cross‐Dehydrogenative Coupling of Quinones with Cyclic Alkanes: One‐Step Access to Parvaquone and its Analogs