56051-00-4Relevant academic research and scientific papers
Site-selective Oxidative Dearomatization of Phenols and Naphthols into ortho-Quinols or Epoxy ortho-Quinols using Oxone as the Source of Dimethyldioxirane
Cabrera-Afonso, María J.,Carre?o, M. Carmen,Urbano, Antonio
supporting information, (2019/08/21)
A novel reactivity of dimethyldioxirane, generated in situ from Oxone and acetone, with substituted phenols and naphthols is reported. This methodology allowed the synthesis of ortho-quinols or epoxy ortho-quinols from a site-selective oxidative dearomatization process, with good yields under very mild conditions. A short total synthesis of natural product lacinilene C methyl ether is also described using this process as the key step. (Figure presented.).
4,5-Dimethyl-2-Iodoxybenzenesulfonic Acid Catalyzed Site-Selective Oxidation of 2-Substituted Phenols to 1,2-Quinols
Uyanik, Muhammet,Mutsuga, Tatsuya,Ishihara, Kazuaki
supporting information, p. 3956 - 3960 (2017/03/27)
A site-selective hydroxylative dearomatization of 2-substituted phenols to either 1,2-benzoquinols or their cyclodimers, catalyzed by 4,5-dimethyl-2-iodoxybenzenesulfonic acid with Oxone, has been developed. Natural products such as biscarvacrol and lacinilene C methyl ether could be synthesized efficiently under mild reaction conditions. Furthermore, both the reaction rate and site selectivity could be further improved by the introduction of a trialkylsilylmethyl substituent at the 2-position of phenols. The corresponding 1,2-quinols could be transformed into various useful structural motifs by [4+2] cycloaddition cascade reactions.
Isolation and synthesis of two antiproliferative calamenene-type sesquiterpenoids from Sterculia tavia from the Madagascar Rain Forest
Dai, Yumin,Harinantenaina, Liva,Brodie, Peggy J.,Callmander, Martin W.,Randrianasolo, Sennen,Rakotobe, Etienne,Rasamison, Vincent E.,Kingston, David G.I.
, p. 6940 - 6944 (2013/01/15)
Investigation of the endemic Madagascan plant Sterculia taiva Baill. (Malvaceae) for antiproliferative activity against the A2780 ovarian cancer cell line led to the isolation of two new bioactive calamenene-type sesquiterpenoids, named tavinin A (2) and
Gossypium Cadinanes and Their Analogues: Synthesis of Lacinilene C, 2,7-Dihydroxycadalene, and Their Methyl Ethers
McCormick, John P.,Shinmyozu, Teruo,Pachlatko, J. Paul,Schafer, Tann R.,Gardner, Jeffrey W.,Stipanovic, Robert D.
, p. 34 - 40 (2007/10/02)
The total synthesis of lacinilene C methyl ether has been accomplished in ten steps with an overall, optimal yield of 38percent by starting with o-methylanisole.Formation of the key α-aryl-α-ketol functionality, which is particularly sensitive to oxidation, was accomplished by stepwise oxidation reactions based on the use of N-methylmorpholine N-oxide/osmium tetraoxide acting on alkene and trimethylsilyl enol ether functionality.Other oxidations could be accomplished by using dichlorodicyanobenzoquinone to generate unsaturation adjacent to the α-ketol group or to form substituted naphtalenes.These reactions permitted adjustment of the oxidation level and oxygenation pattern of the key intermediate, 7-methoxy-α-calacorene (3,4-dihydro-4-isopropyl-7-methoxy-1,6-dimethylnaphthalene), to accomplish the synthesis of 2-hydroxy-7-methoxycadalene, 2,7-dihydroxycadalene, 7-methoxycadalene, and 7-hydroxycadalene, in addition to lacinilene C and its methyl ether.
