1315460-75-3Relevant academic research and scientific papers
PBu3-mediated vinylogous wittig reaction of α-methyl allenoates with aldehydes and mechanistic investigations
Xu, Silong,Chen, Rongshun,He, Zhengjie
experimental part, p. 7528 - 7538 (2011/11/29)
A highly stereoselective PBu3-mediated vinylogous Wittig olefination between α-methyl allenoates and a variety of aldehydes is presented as the first example of a practical and synthetically useful vinylogous Wittig reaction. Mechanistic experiments including deuterium-labeling, intermediate entrapment, and NMR monitoring have been deliberately conducted. On the basis of mechanistic investigations, a reliable mechanism for the vinylogous Wittig reaction is proposed, which features a water/phosphine-coassisted allylic phosphorus ylide 1,3-rearrangement pathway, rather than previous retro-Diels-Alder ones. It is noteworthy that mechanistic findings in this work also provide supportive evidence for typical mechanisms of important phosphine-mediated reactions of allenoates.
Palladium-catalyzed elimination/isomerization of enol triflates into 1,3-dienes
Crouch, Ian T.,Dreier, Timothy,Frantz, Doug E.
, p. 6128 - 6132 (2011/08/05)
Dying to be Dienes: Substituted 1,3-dienes were synthesized by the title reaction (see scheme; Tf=trifluoromethanesulfonyl). Preliminary studies support a mechanistically distinct pathway that involves an initial β-hydride elimination from a cationic vinyl palladium(II) intermediate, a subsequent regiospecific hydropalladation of the corresponding allene intermediate, and a final β-hydride elimination. Copyright
