Is the reaction sequence in phosphine-catalyzed [8+2] cycloaddition controlled by electrophilicity?
Wen-Xuan LinZhuolin PeiCunxi GongHuilin MoKai YangLing-Bo QuDong-Hui WeiJin-Shuai SongShi-Jun LiYu LanPublished in: Chemical communications (Cambridge, England) (2021)
In the presence of multiple electrophiles, the reaction sequence is a critical mechanistic problem. Here, we report a theoretical study on the mechanism of phosphine-catalyzed [8+2] cycloaddition of heptafulvenes and allenoate. DFT calculations showed that electrophilicity is the barrier for nucleophilic attack, while it fails in the prediction of priority.