17245-76-0Relevant academic research and scientific papers
Synthesis of Cyclohexanones through a Catalytic Cationic Cyclization of Alkynols or Enynes
Alonso, Pedro,Fontaneda, Raquel,Pardo, Pilar,Fa?anás, Francisco J.,Rodríguez, Félix
supporting information, p. 1659 - 1662 (2018/03/23)
A novel procedure for the synthesis of cyclohexanones from alkynol or enyne derivatives through a cationic cyclization has been developed. The key points to obtain the six-membered ring derivatives are the use of starting materials containing a terminal alkyne, the use of tetrafluoroboric acid as a promoter of the cationic cyclization, and the appropriate selection of 1,1,1,3,3,3-hexafluoropropan-2-ol (HFIP) as solvent. This strategy can be extended to the biomimetic cationic cyclization of several terpene-derived polyenynes.
Palladium-Catalyzed Conjugate Addition of Arylboronic Acids to β,β-Disubstituted Enones in Aqueous Media: Formation of Bis-benzylic and ortho-Substituted Benzylic Quaternary Centers
Van Zeeland, Ryan,Stanley, Levi M.
, p. 5203 - 5206 (2015/09/15)
Palladium-catalyzed conjugate addition of arylboronic acids to β,β-disubstituted enones in aqueous media is reported. Additions of a wide range of arylboronic acids to β,β-disubstituted enones occur to form ketone products bearing benzylic all-carbon quaternary centers. These reactions are promoted by a simple catalyst prepared from palladium trifluoracetate and 2,2′-bipyridine. The use of aqueous sodium trifluoracetate as the reaction medium significantly enhances reactivity and enables the formation of challenging bis-benzylic and ortho-substituted benzylic all-carbon quaternary centers.
An experimental and theoretical study of the type C enone rearrangement: Mechanistic and exploratory organic photochemistry
Zimmerman, Howard E.,Nesterov, Evgueni E.
, p. 5422 - 5430 (2007/10/03)
We recently described a new photochemical rearrangement which we termed a Type C process. The reaction involves a δ to α aryl migration in 5-disubstituted cyclohexenones also having bulky C-3 substituents. In contrast to most cyclohexenone rearrangements, the reaction occurs via a twisted π-π* excited triplet rather than the usual n-π* state. The electronic nature of the rearrangement was assessed using migration selectivity with p-anisyl and p-cyanophenyl groups. A synthesis of the reactants was elaborated, and the product structures were established by X-ray and NMR analysis. The reaction mechanism was established further with DFT and CASSCF computations. In the latter, localized NBO basis orbitals permitted proper selection of the active space. The nature of the diradical intermediates as well as the transition states was established computationally. Sensitization experiments with regioselectivities the same as those in direct irradiation confirmed the triplet multiplicity of the process.
