Transmetallation Versus β-Hydride Elimination: The Role of 1,4 Benzoquinone in Chelation-Controlled Arylation Reactions with Arylboronic Acids
2012 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 18, no 15, 4714-4722 p.Article in journal (Refereed) Published
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 sigma-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.
Place, publisher, year, edition, pages
Wiley-VCH Verlagsgesellschaft, 2012. Vol. 18, no 15, 4714-4722 p.
Organic Chemistry Theoretical Chemistry
Research subject Chemistry
IdentifiersURN: urn:nbn:se:uu:diva-172740DOI: 10.1002/chem.201102678ISI: 000302162500033OAI: oai:DiVA.org:uu-172740DiVA: diva2:515479