143589-79-1Relevant academic research and scientific papers
Enantioselective Hydrogenation of Endocyclic Enones: the Solution to a Historical Problem?
Lang, Qiwei,Yang, Huaxin,Gu, Guoxian,Feng, Qiang,Wen, Jialin,Zhang, Xumu
, p. 933 - 936 (2021/03/03)
The enantioselective hydrogenation of endocyclic enones has been a historical problem for homogeneous catalysis. We herein report an efficient method to reduce endocyclic enones with molecular hydrogen. Catalyzed by a rhodium/Zhaophos complex, a variety of enones with five-, six- or seven-member ring were hydrogenated with high enantioselectivity (92%—99% ee). Excellent chemo- and enantioselectivity demonstrated this method was successfully applied in the enantioselective hydrogenation of citral to produce enantio-enriched citronellal.
Asymmetric [5+3] formal cycloadditions with cyclic enones through cascade dienamine-dienamine catalysis
Yin, Xiang,Zheng, Yi,Feng, Xin,Jiang, Kun,Wei, Xue-Zhen,Gao, Ning,Chen, Ying-Chun
supporting information, p. 6245 - 6248 (2014/06/23)
A few aminocatalytic modes, such as iminium ions and different dienamines, have provided versatile tools for the functionalization of cyclic enones at various sites. Described here is a previously unreported cascade dienamine/dienamine catalytic pathway for β-substituted 2-cyclopentenones, and even 2-cyclohexenone. It involves domino α′-regioselective Michael addition and a γ-regioselective Mannich reaction with 3-vinyl-1,2-benzoisothiazole-1,1-dioxides to give fused or bridged architectures, which incorporate a spirocyclic skeleton, in excellent stereocontrol, thus furnishing unusual [5+3] formal cycloaddition reactions. Moreover, preliminary biological assays showed that some of the chiral products exhibited promising activity against some cancer cell lines, thus indicating that such skeletons might serve as leads in drug discovery.
Selective Heck reaction of aryl bromides with cyclopent-2-en-1-one or cyclohex-2-en-1-one
Fall, Yacoub,Doucet, Henri,Santelli, Maurice
experimental part, p. 489 - 495 (2009/04/07)
The selective Heck reaction of cyclopent-2-en-1-one or cyclohex-2-en-1-one with aryl bromides gives a simple access to the corresponding 3-arylcycloalk-2-en-1-ones. The choice of the base was found to be crucial to avoid the formation of 3-arylcyclopentan
Synthesis, structure, and antimalarial activity of some enantiomerically pure, cis-fused cyclopenteno-1,2,4-trioxanes
Jefford,Kohmoto,Jaggi,Timari,Rossier,Rudaz,Barbuzzi,Gerard,Burger,Kamalaprija,Mareda,Bernardinelli,Manzanares,Canfield,Fleck,Robinson,Peters
, p. 647 - 662 (2007/10/02)
Two pairs of enantiomerically pure cis-fused cyclopenteno-1,2,4-trioxanes (7, ent-7 and 8, ent-8) are prepared. Their identities are established by dye-sensitized photo-oxygenation of ent-7 and 8 to the allylic hydroperoxides, reduction to the corresponding alcohols, and conversion to the (1S)-camphanoates, the structures of which are determined by X-ray analysis. The dynamic properties of ent-7 are investigated by NMR spectroscopy and PM3 calculations. Evidence for an easily accessible twist-boat conformation is obtained. The in vitro and in vivo antimalarial activities of 7, ent-7, 8, and ent-8 as well as those of the racemic mixtures are evaluated against Plasmodium falciparum, P. berghei, and P. yoelii. No correlation is observed between configuration and activity. Racemates and pure enantiomers have commensurate activities. The mode of action on the intraerythrocytic parasite is rationalized in terms of close docking by the twist-boat conformer of the trioxane on the surface of a molecule of heme, single-electron transfer to the O-O σ* orbital, and scission to the acetal radical which then irreversibly isomerizes to a C-centered radical, the ultimate lethal agent.
