期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 18, 期 15, 页码 4714-4722出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201102678
关键词
arylation; C?C coupling; density functional calculations; elimination; palladium; transmetallation
资金
- Carl Trygger Foundation
- Ake Wiberg Foundation
The formation of an atypical, saturated, diarylated, Heck/Suzuki, domino product produced under oxidative Heck reaction conditions, employing arylboronic acids and a chelating vinyl ether, has been investigated by DFT calculations. The calculations highlight the crucial role of 1,4-benzoquinone (BQ) in the reaction. In addition to its role as an oxidant of palladium, which is necessary to complete the catalytic cycle, this electron-deficient alkene opens up a low-energy reaction pathway from the post-insertion s-alkyl complex. The association of BQ lowers the free-energy barrier for transmetallation of the s-alkyl complex to create a pathway that is energetically lower than the oxidative Heck reaction pathway. Furthermore, the calculations showed that the reaction is made viable by BQ-mediated reductive elimination and leads to the saturated diarylated product.
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