4173-48-2Relevant academic research and scientific papers
Gold(I)-catalysed tandem cyclisation of propargyl acetals and vinyl esters
Siah, Huey-San Melanie,Kaur, Maya,Iqbal, Naseem,Fiksdahl, Anne
, p. 1727 - 1740 (2014)
The results of our previous comparative study of chemoselective gold(I)-catalysed alkene cycloadditions of propargyl substrates demonstrated that propargyl acetals react by different cyclisation pathways from the corresponding esters, and that they also have significantly higher reactivities. To increase understanding of the chemistry of propargyl acetals and to explore the possibilities of generating new compounds through gold(I)-catalysed reactions, a range of reactions of propargyl acetals with vinyl esters have been carried out. A new type of cyclopropyl-cyclopentenyl products, (1,3-dimethoxy-4,5-diphenylcyclopent-2-en-1-yl)-cyclopropyl ester derivatives, was obtained. A plausible mechanism, including sequential [1+2] and [2+3] cycloadditions, is proposed for these highly regio- and stereoselective gold(I)-catalysed reactions. The cyclopentenylation took place stereoselectively, whereas cis/trans mixtures of diastereoisomers were formed in the cyclopropanation step, with the selectivity being controlled by the bulkier vinylic substituent. The tandem reaction allows the construction of polysubstituted and highly functionalised bicyclic compounds. Copyright
Palladium-catalyzed reaction of γ-silylated allyl acetates proceeding through 1,2-shift of a substituent on silicon
Horino, Yoshikazu,Ishibashi, Mayo,Nakasai, Kosuke,Korenaga, Toshinobu
supporting information, (2020/08/28)
The palladium-catalyzed reaction of γ-silylated allyl acetates with water in the presence of CsF induces a previously unprecedented 1,2-shift of a substituent on silicon to produce allylsilanes in situ. The catalytic activity of the palladium increased when using an electron-poor phosphine ligand possessing fluorinated substituents. Further investigation of the reaction revealed that the approximate order of the migratory aptitude of groups from silicon was PhC≡C, allyl > Bn > Ph, vinyl > alkyl (Me, Et). A density functional theory study was employed to explore the reaction mechanism. Finally, the Hosomi–Sakurai-type allylation of aldehydes with in situ-generated α,γ-disubstituted allylsilanes was also investigated.
Gold(I)-Catalysed Tandem Cyclisation of Propargyl Acetals and Vinyl Esters
Siah, Huey-San Melanie,Kaur, Maya,Iqbal, Naseem,Fiksdahl, Anne
, p. 1727 - 1740 (2015/10/05)
The results of our previous comparative study of chemoselective gold(I)-catalysed alkene cycloadditions of propargyl substrates demonstrated that propargyl acetals react by different cyclisation pathways from the corresponding esters, and that they also have significantly higher reactivities. To increase understanding of the chemistry of propargyl acetals and to explore the possibilities of generating new compounds through gold(I)-catalysed reactions, a range of reactions of propargyl acetals with vinyl esters have been carried out. A new type of cyclopropyl-cyclopentenyl products, (1,3-dimethoxy-4,5-diphenylcyclopent-2-en-1-yl)-cyclopropyl ester derivatives, was obtained. A plausible mechanism, including sequential [1+2] and [2+3] cycloadditions, is proposed for these highly regio- and stereoselective gold(I)-catalysed reactions. The cyclopentenylation took place stereoselectively, whereas cis/trans mixtures of diastereoisomers were formed in the cyclopropanation step, with the selectivity being controlled by the bulkier vinylic substituent. The tandem reaction allows the construction of polysubstituted and highly functionalised bicyclic compounds.
