Oxidative Coupling of Phenols and Phenol Ethers

Whiting, Donald A.

doi:10.1016/b978-0-08-052349-1.00076-7

Cited by 42 publications

(22 citation statements)

References 165 publications

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“…For the biaryl bond formation we selected the phenol oxidative coupling process, 13 which is a powerful method of proven utility in synthesis and is also involved in a myriad of biogenetic routes to natural products. Attempts to emulate Nature using a wide variety of reagents (HRP, TTFA, PIFA, MoCl 5 , VOCl 3 , Ce (OH) 4 , etc.)…”

Section: Resultsmentioning

confidence: 99%

“…1 H-NMR (400.13 MHz, CD 3 OD) (data for monomer) δ 7.2-7.1 (m, 2H, ArH), 6.82 (d, J = 8.7 Hz, 1H, ArH), 5.01 (br s, 2H, OH), 3.89 (s, 2H, 2H3), 3.78 (s, 3H, OCH 3 ) ppm. 13 (13). LiOH (0.22 g, 5.22 mmol) was added to a solution of ester 12 (0.10 g, 0.17 mmol) in THF-H 2 O (1 : 1 v/v, 0.58 mL).…”

Section: Discussionmentioning

confidence: 99%

“…1 H-NMR (400.13 MHz, CD 3 OD) (data for monomer) δ 7.43 (d, J = 1.9 Hz, 1H, ArH), 7.07 (d, J = 1.9 Hz, 1H, ArH), 3.85 (s, 2H, 2H3) ppm. 13 C-NMR (100.61 MHz, CD 3 OD) (data for monomer) δ 165.4 (s), 150.5 (s), 149.4 (s), 132.5 (d) 2,2′-(5,5′-Dibromo-6,6′-dihydroxybiphenyl-3,3′-diyl)diacetonitrile (15). To a solution of 13 (0.02 g, 0.04 mmol) in CH 2 Cl 2 (0.4 mL) were added HOBt (0.01 g, 0.08 mmol) and 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide hydrochloride (EDCI, 0.02 g, 0.08 mmol) at 0 °C, followed by a solution of 3bromotyramine hydrochloride (14) (0.02 g, 0.15 mmol) and diisopropylethylamine (0.03 mL, 0.15 mmol) in DMF (0.5 mL).…”

Section: Discussionmentioning

confidence: 99%

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First total synthesis of dioxepine bastadin 3

2012

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The synthesis of dioxepine bastadin 3, a tyrosine-tyramine derivative with a dibenzo-1,3-dioxepine scaffold that is rarely present among natural products, is described. The dibenzo-1,3-dioxepine ring was formed early in the sequence and the (E)-2-(hydroxyimino)-N-alkylamide was generated in the last step by oxidation of the 2-amino-N-alkylamide precursor. The presumably biogenetic late-stage ring formation starting from congener bastadin 3 failed. A new synthesis of this alkaloid was also developed. This new route requires a minimal use of protecting groups and the order of the two key steps was reversed relative to the route to dioxepine bastadin 3.

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Section: Resultsmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

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First total synthesis of dioxepine bastadin 3

2012

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“…32 Phenols or phenolate ions are easily oxidized to cation radicals or phenoxy radicals. 33 the negative charge or radical is stabilized by delocalization into the ring. the aryloxy radical may be formed either directly from phenol by loss of H • or by loss of one electron from the corresponding phenolate.…”

Section: Solution/gas Phase Reactivity For Phenolic Compoundsmentioning

confidence: 99%

Gas-Phase Reactivity of Acylphenols in Electrospray and Matrix-Assisted Laser Desorption Ionization Mass Spectrometry

Schmitz-Afonso¹,

Guérineau²,

Maia‐Grondard³

et al. 2009

Eur J Mass Spectrom (Chichester)

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Acylphenols from Myristica crassa were identified based on liquid chromatography high-resolution mass spectrometry and liquid chromatography tandem mass spectrometry (MS/MS) experiments. Two types of compound were found in the extract of the plant: monomeric (malabaricone B and C) and dimeric compounds (C-C bonded biphenyl and C-C bonded phenyl-linear carbon chain). Evidence of formation of covalent dimeric ions during the electrospray ionization and matrix-assisted laser desorption ionization (MALDI) processes was established. [2M-3H](-) dimeric ions were detected on the mass spectra of each monomeric compound during high-performance liquid chromatography separation. The MS/MS spectra of those species were compared to the MS/MS spectra obtained for the dimeric compounds synthesized by the plant. Fragmentation pathways were studied for the two classes of dimer. The dimeric ions formed in the ion source were C-C bonded biphenyl compounds. Further evidence was obtained from MALDI experiments: increase in the extraction delay time leads to an increase of the dimeric ions relative abundance. Their formation is based on the high reactivity of phenols or phenolate ions which are easily oxidized yielding phenoxy radicals.

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“…A large number of reviews have previously been published in the field of oxidative coupling reactions [11,[20][21][22][23][24][25][26]. In this chapter, current thinking on the different mechanisms involved in these types of reactions and the most recent developments in this field will be presented.…”

Section: Introductionmentioning

confidence: 99%

Oxidative Aryl‐Coupling Reactions in Synthesis

Lessène

Feldman

2002

Modern Arene Chemistry

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The oxidant-mediated coupling of electron-rich arene rings has served over several decades as a valuable procedure to access biaryl units. The complex mixtures of isomers that often plagued the earliest studies have gradually given way to synthetically useful product distributions upon application of more selective coupling protocols. Continual advances in the nature of the oxidant (and its attendant ligands) and more precisely defined reaction conditions have led to increasing levels of control upon CaC bond formation. Chemoselective (CaC vs. CaO bond formation with phenols; suppression of product oxidation), regioselective (o-o 0 , vs. o-p 0 vs. p-p 0 CaC bond formation), and, more recently, stereoselective (atropisomer-selective) biaryl bond formation can now be achieved in many well-defined systems. A survey of the more recent advances in these areas is presented.14.1

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Oxidative Coupling of Phenols and Phenol Ethers

Cited by 42 publications

References 165 publications

First total synthesis of dioxepine bastadin 3

First total synthesis of dioxepine bastadin 3

Gas-Phase Reactivity of Acylphenols in Electrospray and Matrix-Assisted Laser Desorption Ionization Mass Spectrometry

Oxidative Aryl‐Coupling Reactions in Synthesis

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