7691-31-8Relevant 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
scheme or table, 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.
