180475-48-3Relevant academic research and scientific papers
Intramolecular azide-alkene 1,3-dipolar cycloaddition/enamine addition(s) cascade reaction: Synthesis of nitrogen-containing heterocycles
De Miguel, Irene,Herradon, Bernardo,Mann, Enrique
supporting information; experimental part, p. 1731 - 1736 (2012/07/28)
A cascade intramolecular azide-alkene 1,3-dipolar cycloaddition/1,2 enamine and/or 1,4 enamine addition reaction sequence has been developed, and provides access to a variety of nitrogen containing heterocycles from readily available ω-azido alkenes. Copy
Copper-catalyzed asymmetric conjugate addition of trialkylaluminium reagents to trisubstituted enones: Construction of chiral quaternary centers
Vuagnoux-D'Augustin, Magali,Alexakis, Alexandre
, p. 9647 - 9662 (2008/12/21)
Me3Al, Et1Al, and vinylalane species undergo enantioselective conjugate addition to a wide range of 2- or 3-substituted enones (cyclopent-2enones, cyclohex-2-enones, 3-methyl cyclohept-2-enone) in the presence of catalytic amount of copper salt (copper thiophene carboxylate, [Cu(CH3-CN)4]BF4 or [CuOTf]2· C6H6) and tropos-phosphoramidite-based ligand. Thus, chiral quaternary centers can be built, with up to 98% ee after rigorous optimization of experimental conditions. It was shown that the main important parameter was the order of the introduction of the reagents. Then, the generated enantioenriched aluminium enolates and the chiral conjugate adducts were functionalized and used for subsequent reactions.
Formaldehyde dialkylhydrazones as neutral formyl anion and cyanide equivalents: Nucleophilic addition to conjugated enones
Diez,Fernandez,Gasch,Lassaletta,Llera,Martin-Zamora,Vazquez
, p. 5144 - 5155 (2007/10/03)
A versatile methodology for the nucleophihc formylation and cyanation of conjugated enones is reported. The procedure is based on the use of formaldehyde dimethylhydrazone, which, acting as a neutral formyl anion equivalent, adds to preformed trialkylsilyl-enone complexes. Both 4-(silyl- oxy)-3-enal hydrazones 3 or deprotected 4-oxo aldehyde monohydrazones 4 can be obtained at products depending on quenching conditions. In full analogy, an asymmetric version of the reaction using chiral formaldehyde SAMP- hydrazone as a neutral synthon of the chiral formyl anion has been developed, giving rise to the corresponding adducts 5 and 6 in good yields and with excellent diastereoselectivities (de 85-≤98%). Ozonolysis or HCl-mediated hydrolysis of adducts 4 and 6 readily affords racemic and optically enriched 4-oxo aldehydes 7, respectively. Additionally, high-yielding MMPP-oxidative cleavage of 4-oxo hydrazones 4 and 6 has been performed to obtain 4-oxo nitriles 8 in racemic and optically enriched forms, respectively. In this way, interesting chiral bifunctional building blocks, some of them bearing newly created stereogenic quaternary centers, have been efficiently synthesized.
REACTION OF METHYL-SUBSTITUTED 7-CHLORO- AND 7,7-DICHLOROBICYCLOheptan-2-ones WITH SODIUM METHOXIDE AND THIOPHENOLATE
Kulinkovich, O. G.,Tishchenko, I. G.,Romashin, Yu. N.
, p. 81 - 85 (2007/10/02)
The reaction of exo-7-chloro-6-methylbicycloheptan-2-one, exo-7-chloro-4,4,6-trimethylbicycloheptan-2-one, 7,7-dichloro-6-methylbicyclo-heptan-2-one, and 7,7-dichloro-4,4,6-trimethylbicycloheptan-2-one with sodium methoxide takes place with opening of the cyclopropane ring and the formation of the corresponding 3-dimethoxymethyl- and 3-trimethoxymethylcyclohexanones.The reaction with sodium thiophenolate leads to the product from substitution of the exo-chlorine atom by the phenylthio group with retention of the three-membered ring.
