490-06-2Relevant articles and documents
A Catalyst-Controlled Aerobic Coupling of ortho-Quinones and Phenols Applied to the Synthesis of Aryl Ethers
Huang, Zheng,Lumb, Jean-Philip
supporting information, p. 11543 - 11547 (2016/11/17)
ortho-Quinones are underutilized six-carbon-atom building blocks. We herein describe an approach for controlling their reactivity with copper that gives rise to a catalytic aerobic cross-coupling with phenols. The resulting aryl ethers are generated in high yield across a broad substrate scope under mild conditions. This method represents a unique example where the covalent modification of an ortho-quinone is catalyzed by a transition metal, creating new opportunities for their utilization in synthesis.
Enantioselective synthesis of bicyclo[2.2.2]octenones using a copper-mediated oxidative dearomatization/[4 + 2] dimerization cascade
Dong, Suwei,Zhu, Jianglong,Porco Jr., John A.
, p. 2738 - 2739 (2008/09/19)
An enantioselective approach to bicyclo[2.2.2]octenone structures utilizing a copper-mediated asymmetric oxidative dearomatization/[4 + 2] dimerization cascade is described. The total synthesis and absolute stereochemistry reassignment of (+)-aquaticol has been achieved using the methodology. Copyright
Regio- and stereoselectivities in Diels-Alder cyclodimerizations of orthoquinonoid cyclohexa-2,4-dienones
Gagnepain, Julien,Méreau, Rapha?l,Dejugnac, Delphine,Léger, Jean-Michel,Castet, Frédéric,Deffieux, Denis,Pouységu, Laurent,Quideau, Stéphane
, p. 6493 - 6505 (2008/02/08)
The [4+2] cyclodimerization of cyclohexa-2,4-dienone derivatives of the orthoquinone monoketal and orthoquinol types has been the topic of numerous investigations over the last 50 years in the aim of rationalizing the extraordinary level of regio-, site-,
Efficient access to orthoquinols and their [4 + 2] cyclodimers via SIBX-mediated hydroxylative phenol dearomatization
Lebrasseur, Nathalie,Gagnepain, Julien,Ozanne-Beaudenon, Aurelie,Leger, Jean-Michel,Quideau, Stephane
, p. 6280 - 6283 (2008/02/10)
(Chemical Equation Presented) SIBX, the nonexplosive formulation of the λ5-iodane 2-iodoxybenzioc acid (IBX), safely and efficiently mediates the hydroxylative dearomatization of various 2-alkylphenols and napthols into orthoquinols or their [4 + 2] cyclodimers. Reactions are typically run at room temperature using SIBX as a suspension in THF. Using these conditions, natural products such as the cyclodimer of the terpene carvacrol and, for the first time, the shikimate-derived (±)-grandifloracin were prepared in one step from their respective phenolic precursor.
Total synthesis of (+)-aquaticol by biomimetic phenol dearomatization: Double diastereofacial differentiation in the Diels-Alder dimerization of orthoquinols with a C2-symmetric transition state
Gagnepain, Julien,Castet, Frederic,Quideau, Stephane
, p. 1533 - 1535 (2008/04/05)
(Chemical Equation Presented) Double or nothing: The bissesquiterpene (+)-aquaticol was synthesized by biomimetic oxidative dearomatization of 1 via an orthoquinol intermediate that undergoes spontaneous and selective dimerization; only like diastereomers
Photo-irradiation of α-halo carbonyl compounds: A novel synthesis of α-hydroxy- and α,α′-dihydroxyketones
Chai, Wen,Takeda, Akihiro,Hara, Makoto,Ji, Shun-Jun,Horiuchi, C. Akira
, p. 2453 - 2463 (2007/10/03)
The reaction of α-halo ketones (α-iodocycloalkanones, α-bromocycloalkanones, α-iodo-β-alkoxy esters, and α-iodoacyclicketones) with irradiation under a high-pressure mercury lamp gave the corresponding α-hydroxyketones in good yields. For α-bromoketones, it was found that α-hydroxylation does not occur. However, α-bromoketones were converted into α-hydroxyketones in the presence of KI. In the case of α,α′-diiodo ketones, α,α′-dihydroxyketones, which up to now have scarcely been reported, were obtained. This reaction affords a new, clean and convenient synthetic method for α-hydroxy- and α,α′- dihydroxyketones.
The formation of orthoquinones in the dimethyldioxirane oxidation of phenols
Crandall, Jack K.,Zucco, Martine,Scott Kirsch,Coppert, David M.
, p. 5441 - 5444 (2007/10/02)
The dimethyldioxirane oxidation of selected phenols provides the corresponding orthoquinones. This conversion proceeds via the related arenediols, which are cleanly oxidized to the quinones by this oxidant.
