![1,7-bis(trimethylsiloxy)bicyclo[5.1.0]octane](/Databaselist/images/loading.webp)
935-29-5Relevant academic research and scientific papers
A mild, large-scale synthesis of 1,3-cyclooctanedione: Expanding access to difluorinated cyclooctyne for copper-free click chemistry
Sims, Evan A.,DeForest, Cole A.,Anseth, Kristi S.
, p. 1871 - 1873 (2011)
We report the large-scale synthesis of 1,3-cyclooctanedione in five steps with 29% yield. This molecule is a synthetic precursor to difluorinated cyclooctyne, which participates in a bioorthogonal copper-free click reaction with azides. The final step demonstrates the first successful application of the Wacker-Tsuji oxidation to form a cyclic 1,3-dione.
Constrained bithiazoles: Small molecule correctors of defective δf508-CFTR protein trafficking
Coffman, Keith C.,Nguyen, Huy H.,Phuan, Puay-Wah,Hudson, Brandi M.,Yu, Gui J.,Bagdasarian, Alex L.,Montgomery, Deanna,Lodewyk, Michael W.,Yang, Baoxue,Yoo, Choong L.,Verkman,Tantillo, Dean J.,Kurth, Mark J.
, p. 6729 - 6738 (2014/10/15)
Conformationally constrained bithiazoles were previously found to have improved efficacy over nonconstrained bithiazoles for correction of defective cellular processing of the δF508 mutant cystic fibrosis transmembrane conductance regulator (CFTR) protein. In this study, two sets of constrained bithiazoles were designed, synthesized, and tested in vitro using δF508-CFTR expressing epithelial cells. The SAR data demonstrated that modulating the constraining ring size between 7-versus 8-membered in these constrained bithiazole correctors did not significantly enhance their potency (IC50), but strongly affected maximum efficacy (Vmax), with constrained bithiazoles 9e and 10c increasing Vmax by 1.5-fold compared to benchmark bithiazole corr4a. The data suggest that the 7-and 8-membered constrained ring bithiazoles are similar in their ability to accommodate the requisite geometric constraints during protein binding.
Fragmentation of tertiary cyclopropanol compounds catalyzed by vanadyl acetylacetonate
Kirihara, Masayuki,Kakuda, Hiroko,Ichinose, Motohiro,Ochiai, Yuta,Takizawa, Shinobu,Mokuya, Asuka,Okubo, Kumiko,Hatano, Akihiko,Shiro, Motoo
, p. 4831 - 4839 (2007/10/03)
Tertiary cyclopropanol compounds react with a catalytic amount of vanadyl acetylacetonate in the presence of oxygen affording β-hydroxyketones and β-diketones. For 3-substituted-bicyclo[4.1.0]alkanols, peroxides are obtained, as are the β-hydroxyketones. Conversely, 2- ethoxycarbonylcyclopropyl silyl ethers produce ethyl γ-oxocarboxylate derivatives given the same reaction conditions.
Synthetic Applications in Radical/Radical Cationic Cascade Reactions
Rinderhagen, Heiko,Mattay, Jochen
, p. 851 - 874 (2007/10/03)
Oxidative photoinduced electron transfer (PET) reactions have been performed with various cyclic cyclopropyl(vinyl) silyl ethers bearing an olefinic or acetylenic side chain. The reactions result in bi- to tetracyclic ring systems via a fragmentation-radical/radical cationic addition reaction pathway with well defined ring juncture. The mode of cyclisation (endo/exo) can be partially controlled by addition of nucleophiles due to the suppression of radical cationic reaction pathways. Quantum chemical calculation of the cyclisation transition states underline the experimentally found selectivities. Additional mechanistic studies concerning the saturation step reveal that the final radical is saturated mostly by the solvent and traces of water in the solvent.
Ambident Reactivity of Medium-Ring Cycloalkane-1,3-dione Enolates
Thompson, Glenn S.,Hirsch, Jerry A.
, p. 1098 - 1101 (2007/10/03)
Cycloalkane-1,3-diones with ring sizes 7-10 have been converted to their enolates and subjected to a variety of ethylation and methylation reagent/solvent systems. The greatest amount of O-alkylation was encountered using ethyl tosylate in HMPA. The O/C alkylation ratios decreased with almost every reagent/solvent system as the ring size was increased. This trend is consistent with greater steric strain in the conjugated enolate resonance contributor, resulting in diminished O-attack as the ring size is increased.
Tertiary cyclopropanol systems as synthetic intermediates: Novel ring-cleavage of tertiary cyclopropanol systems using vanadyl acetylacetonate
Kirihara, Masayuki,Ichinose, Motohiro,Takizawa, Shinobu,Momose, Takefumi
, p. 1691 - 1692 (2007/10/03)
Tertiary cyclopropanol systems react with a catalytic amount of vanadyl acetylacetonate under an oxygen atmosphere to afford β-hydroxyketones and β-diketones.
Palladium(0)-catalyzed isomerization of α,β-epoxy ketones to β-diketones
Suzuki, M.,Watanabe, A.,Noyori, R.
, p. 230 - 236 (2007/10/02)
In the presence of catalytic amounts of tetrakis(triphenylphosphine)palladium(0) and 1,2-bis(diphenylphosphino)ethane, α,β-epoxy ketones isomerize to the corresponding β-diketones in high yields.Both open-chain and cyclic substrates can be used.Possible reaction mechanisms are discussed.
Mechanism of Intramolecular Photocycloadditions of Cyclooctenones
Pirrung, Michael C.,Webster, Nicholas J. G.
, p. 3603 - 3613 (2007/10/02)
The intramolecular photochemical cycloadditions of a number of 4'-substituted (3'-butenyloxy)-cyclooctenones have been studied.Two classes of substrates were found.One class (phenyl- and vinyl-substituted) forms adducts in an efficient reaction, while the rest of the compounds from photoproducts slowly and in low yield.The behavior of a carbon analogue shows that rotational relaxation of the cyclooctenone triplet is faster than cycloaddition.Based on quenching and sensitization studies, it has been suggested that the substituent effect is indicative of an enhanced rate of cyclization to form a 1,4-biradical.
CYCLOOCTENONE PHOTOCYCLOADDITIONS
Pirrung, Michael C.,Webster, Nicholas J.G.
, p. 3983 - 3986 (2007/10/02)
The first intramolecular photocycloadditions of cyclooctenones have been achieved using substituted 3-butenyloxy cyclooctenones.
A FACILE SYNTHESIS OF 1,3-CYCLOALKADIONES
Nishiguchi, Ikuzo,Hirashima, Tsuneaki,Shono, Tatsuya,Sasaki, Manji
, p. 551 - 554 (2007/10/02)
1,3-Cycloalkadiones were prepared by the reaction of 1,2-bis(trimethylsiloxy)cycloalkenes with chloromethyl methyl ether followed by treatment of the resulting 2-hydroxy-2-methoxymethyl cycloalkanones with potassium hydrogen sulfate.The first step of the reactions was effectively catalyzed by active zinc reagents prepared from zinc-copper and alkyl iodides.
