Disease relevance of Dimethyldioxirane

• Mechanisms of killing of spores of Bacillus subtilis by dimethyldioxirane [1].

High impact information on Dimethyldioxirane

• Glycals were attached to a polystyrene copolymer with a silyl ether bond and were activated to function as glycosyl donors with 3,3-dimethyldioxirane [2].
• The sigma(C-C) activation of 3 with DMD (Delta G(*) = 23.9 kcal mol(-1) and Delta G(r) = -5.4 kcal mol(-1)) is the first example of a molecule-induced homolytic C-C bond cleavage [3].
• It was found recently that 17beta-estradiol (E2) could be activated by the epoxide-forming oxidant dimethyldioxirane (DMDO) resulting in the inhibition of rat liver nuclear and nucleolar RNA synthesis in vitro (Carcinogenesis, 17, 1957-1961, 1996) [4].
• Treatment of highly potent and densely functionalized bryostatin analogue 1 with dimethyldioxirane afforded the C-9 hydroxylated hemiketal 2 via oxyfunctionalization of the C9-CH bond, one of 12 CH bonds geminal to an oxygen substituent in 1 [5].
• Dimethyldioxirane effects the remarkable one-step deprotection/oxidative cyclization of an eight-membered ring amino-ketone to the unique hydroxylamine hemiketal ring system that is a distinctive structural motif of FR900482 [6].

Biological context of Dimethyldioxirane

• Oxidation of nitrobenzylic carbanions with dimethyldioxirane. new synthesis of quinomethanes and nitrobenzylic carbinols. First examples of methylation of carbanions with dimethyldioxirane [7].

Associations of Dimethyldioxirane with other chemical compounds

• Activation of 17beta-estradiol and estrone by dimethyldioxirane and inhibition of rat liver nuclear and nucleolar RNA synthesis in vitro [8].
• Oxidation of 30a with saccharine-derived oxaziridine 21 for fumiquinazolines A and B and oxidation of 30b with dimethyldioxirane for fumiquinazoline I selectively formed the appropriate imidazoindolone stereoisomers [9].
• Key reactions are a NaH-promoted intramolecular cyclization of an alkynylamide to form a gamma-lactam, an aldol reaction of a benzylidene-substituted ketone, and the late-stage introduction of the benzoyl group by a selective oxidation of a benzylidene moiety with dimethyldioxirane (DMD) [10].

Gene context of Dimethyldioxirane

• However, after reacting with dimethyldioxirane (DMDO), a versatile epoxide-forming oxidant, these estrogens were able to inhibit and in a dose-dependent manner nuclear and nucleolar RNA synthesis in vitro [8].
• The total energy (CBS-APNO) of DMDO is 2.6 kcal/mol lower than that of isomeric 1,2-dioxacyclopentane that has an estimated SE of 5 kcal/mol [11].
• Alkyl substitutents have a meaningful effect upon the SE of small ring compounds. gem-Dimethyl substitution lowers the strain energy of cyclopropanes, cyclobutanes, epoxides, and dimethyldioxirane (DMDO) by 6-10 kcal/mol relative to an unbranched acyclic reference molecule [11].

Analytical, diagnostic and therapeutic context of Dimethyldioxirane

• [reaction: see text] The oxidation of 7,8-dithiabicyclo[4.2.1]nona-2,4-diene 7-exo-oxide with dimethyldioxirane (DMD) provided the 7-exo-8-exo-dioxide, the structure of which was determined by X-ray crystallography [S-S 2.341(2) A and 90 degree angle O-S-S-O 4.1(3) degrees ] [12].

References