ortho-Arylation of 3,5-di-tert-butylphenol with aryllead(IV) derivatives: a facile synthesis of sterically hindered phenols

Barton, D. H. R.; Donnelly, Dervilla M. X.; Guiry, Patrick J.; Finet, Jean‐Pierre

doi:10.1039/p19940002921

Cited by 19 publications

(12 citation statements)

References 19 publications

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“…85,86 Furthermore, Bi(V) phenoxides have been isolated and characterized for electron-poor phenols, and have been shown to undergo ligand coupling upon heating. 87 The divergent chemoselectivity exhibited by bismacycles 50 and 51 has parallels in other systems based on bismuth(V), 60 iodine(III) 88,89 and lead(IV), 90,91 each of which engage phenols in either oxidation or aryl-transfer processes as a function of the ligands at the metal center. 13 While the basicity of the ligands associated with Bi(V) clearly differentiates 50 and 51, the dimeric nature of the former may also contribute to the observed chemoselectivity differences.…”

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confidence: 87%

Modular bismacycles for the selective C–H arylation of phenols and naphthols

et al. 2020

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Given the important role played by 2-hydroxybiaryls in organic, medicinal and materials chemistry, concise methods for the synthesis of this common motif are extremely valuable. In seeking to extend the synthetic chemists' lexicon in this regard, we have developed an expedient and general strategy for the ortho-arylation of phenols and naphthols using readily-available boronic acids. Our methodology relies on in situ generation of a uniquely reactive Bi(V) arylating agent from a benchstable Bi(III) precursor via telescoped B-to-Bi transmetallation and oxidation. By exploiting reactivity

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confidence: 87%

Modular bismacycles for the selective C–H arylation of phenols and naphthols

et al. 2020

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“…A related rearrangement within this category is the migration of aryl groups from phenolate–metal complexes (Scheme ). Barton introduced Pb(IV) and Bi(V) reagents for this purpose as early as 1985. More recently, Yamamoto reported asymmetric variants that employ chiral amine ligands to install biaryl bonds with good atroposelectivity .…”

Section: C2 Functionalizationmentioning

confidence: 99%

Phenol-Directed C–H Functionalization

2018

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Phenols are important starting materials, intermediates, and functional elements of a very broad range of chemicals and materials. They are large-volume products of benzene oxidation and are increasingly available from biomass. Investment in methodologies that improve the efficiency of their use can have both immediate and future impacts on chemical upgrading. This review summarizes recent phenol-directed C–H functionalization reactions, which provide efficient increases in molecular complexity. Catalytic methodologies play an increasingly important role in addressing long-standing challenges of chemo- and regioselectivity, setting the stage for increased use of phenols in fine-chemical synthesis. We discuss these advances while underscoring persistent challenges, with the goal of motivating increased interest in this versatile functional group.

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“…To illustrate the effect of acetyl groups of arylleads on the enantioselectivity, 2-isopropylphenyllead tribenzoate (13) was prepared from lead tetrabenzoate 25 by the procedure described by Pinhey. 21c The reaction between aryllead tribenzoate 13 and a Unless otherwise specified, reactions were performed using lithiated phenol (1 equiv), aryllead (2.5 equiv), MS 4 Å (3 g/mmol), brucine (6 equiv) in toluene.…”

Section: Phenol or Aniline Coupling With Aryllead Triacetatesmentioning

confidence: 99%

“…13 The reaction using arylleads as an equivalent of aryl cation was originally devised by Pinhey, who demonstrated that the use of excess pyridine accelerated the reaction rate (Scheme 1). 14 In marked contrast, anilines and anilides do not undergo either C-or N-arylation with aryllead triacetates.…”

Section: Introductionmentioning

confidence: 99%

Asymmetric Carbon−Carbon Coupling of Phenols or Anilines with Aryllead Triacetates

et al. 2002

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The asymmetric coupling of various phenol or aniline derivatives with bulky aryllead triacetates was thoroughly investigated using optically active amines, including strychnine and brucine. We found that conformationally restricted tertiary amines, as well as lithium aryloxides and molecular sieves, are essential for accelerating the rate of phenol coupling. Consequently, the reaction can be carried out at a low temperature (-40 to -20 degrees C) and gives a high degree of diastereo- and enantioselectivity. In contrast to the effectiveness of lithiation in phenol coupling, magnesation of anilines was a critical technique for aniline coupling with aryllead triacetates. Using these coupling methods, a diverse set of di-, tri, and polyaryl compounds with axial chirality can be easily obtained, and these should be useful for the construction of a variety of aryl-aryl frameworks involved in metal ligands, natural products, and artificial helical polymers.

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ortho-Arylation of 3,5-di-tert-butylphenol with aryllead(IV) derivatives: a facile synthesis of sterically hindered phenols

Cited by 19 publications

References 19 publications

Modular bismacycles for the selective C–H arylation of phenols and naphthols

Modular bismacycles for the selective C–H arylation of phenols and naphthols

Phenol-Directed C–H Functionalization

Asymmetric Carbon−Carbon Coupling of Phenols or Anilines with Aryllead Triacetates

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