3117-02-0Relevant articles and documents
Helical-Shaped Bis-1,4-benzoxathiines through an Inverse-Electron-Demand Hetero-Diels–Alder Reaction of ortho-Thioquinones
Viglianisi, Caterina,Menichetti, Stefano,Piantini, Sara,Tofani, Lorenzo
, p. 5386 - 5392 (2016)
The reaction of transient ortho-thioquinones, which act as electron-poor dienes, with properly designed bis-dienophiles leads to the formation of helical-shaped bis-benzoxathiine cycloadducts with complete control of the regiochemistry and the relative stereochemistry. Bis-benzoxathiines were the result of two consecutive inverse-electron-demand cycloaddition processes with stereospecific approach of the diene anti to the bis-dienophile. The helical-shaped structure of the final products was demonstrated spectroscopically and confirmed by single-crystal X-ray analysis.
Polyoxometalate-based supramolecular porous frameworks with dual-active centers towards highly efficient synthesis of functionalized: P -benzoquinones
An, Haiyan,Chang, Shenzhen,Chen, Yanhong,Huang, Yaohui,Luo, Huiyun,Zhu, Qingshan
, p. 8591 - 8603 (2021/11/17)
Selective oxidation of substituted phenols is an ideal method for preparing functionalized p-benzoquinones (p-BQs), which serve as versatile raw materials for the synthesis of a variety of biologically active compounds. Herein, two new polyoxometalate-based supramolecular porous frameworks, K3(H2O)4[Cu(tza)2(H2O)]2[Cu(Htza)2(H2O)2][BW12O40]·6H2O (1) and H3K3(H2O)3[Cu(Htza)2(H2O)]3[SiW12O44]·14H2O (2) (Htza = tetrazol-1-ylacetic acid), were synthesized and structurally characterized by elemental analysis, infrared spectroscopy, thermal analysis, UV-vis diffuse reflectance spectroscopy, and single-crystal X-ray and powder diffraction. The single-crystal X-ray diffraction analysis indicates that both compounds possess unique petal-like twelve-nucleated Cu-organic units composed of triangular and hexagonal metal-organic loops. In 1, the Cu-organic units are isolated and [BW12O40]5- polyoxoanions are sandwiched between staggered adjacent triangular channels in the structure. However in 2, the Cu-organic units extend into a two-dimensional layered structure, and the [SiW12O44]12- polyoxoanions occupy the larger hexagonal channels in the stacked structure. Both compounds as heterogeneous catalysts can catalyze the selective oxidation of substituted phenols to high value-added p-BQs under mild conditions (60 °C) with TBHP as the oxidant, particularly in the oxidation of 2,3,6-trimethylphenol to 2,3,5-trimethyl-p-benzoquinone (TMBQ, key intermediate in vitamin E production). Within 8-10 min, the yield of TMBQ is close to 100%, and oxidant utilization efficiency is up to 94.2% for 1 and 90.9% for 2. The turnover frequencies of 1 and 2 are as high as 5000 and 4000 h-1, respectively. No obvious decrease in the yield of TMBQ was observed after five cycles, which indicates the excellent sustainability of both compounds. Our study of the catalytic mechanism suggests that there is a two-site synergetic effect: (i) the copper ion acts as the catalytic site of the homolytic radical pathway; and (ii) the polyoxoanion acts as the active center of the heterolytic oxygen atom transfer pathway. This journal is
Bioinspired Total Synthesis of Bussealin e
Twigg, David G.,Baldassarre, Leonardo,Frye, Elizabeth C.,Galloway, Warren R. J. D.,Spring, David R.
supporting information, p. 1597 - 1599 (2018/03/23)
The first total synthesis of bussealin E, a natural product with a unique cycloheptadibenzofuran scaffold, is reported. A strategy inspired by a proposed biosynthesis was employed whereby a diphenylpropane derivative underwent an oxidative phenolic coupling to forge the tetracyclic ring system. The synthesis of the diphenylpropane featured a key sp2-sp3 Hiyama coupling between a vinyldisiloxane and a benzylic bromide.
Photochromic coenzyme Q derivatives: Switching redox potentials with light
Simeth, Nadja A.,Kneuttinger, Andrea C.,Sterner, Reinhard,K?nig, Burkhard
, p. 6474 - 6483 (2017/08/29)
Coenzyme Q is an important redox cofactor involved in a variety of cellular processes, and is thus found in several cell compartments. We report a photochromic derivative of coenzyme Q that combines the molecular structures of the redox active cofactor and a photochromic dye. Light irradiation triggers an electronic rearrangement reversibly changing the redox potential. We used this effect to control the intermolecular redox reaction of the photochromic coenzyme Q derivative with dihydropyridine in solution by light irradiation. On mitochondria, the altered redox properties showed an effect on the respiratory chain. The experiments demonstrate that the redox reactions can be initiated inside the system of interest through irradiation with light and the accompanied photoisomerization.
