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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 Lan
Published 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.
Keyphrases
  • density functional theory
  • room temperature
  • molecular dynamics
  • molecular dynamics simulations
  • electron transfer
  • ionic liquid
  • monte carlo