Regioselective Isomerization of Terminal Alkenes Catalyzed by a PC(sp3)Pincer Complex with a Hemilabile Pendant Arm

Sophie De-Botton, D. Sc Oleg A. Filippov, Elena S. Shubina, Natalia V. Belkova*, Dmitri Gelman*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

8 Scopus citations

Abstract

We describe an efficient protocol for the regioselective isomerization of terminal alkenes employing a previously described bifunctional Ir-based PC(sp3)complex (4) possessing a hemilabile sidearm. The isomerization, catalyzed by 4, results in a one-step shift of the double bond in good to excellent selectivity, and good yield. Our mechanistic studies revealed that the reaction is driven by the stepwise migratory insertion of Ir−H species into the terminal double bond/β-H elimination events. However, the selectivity of the reaction is controlled by dissociation of the hemilabile sidearm, which acts as a selector, favoring less sterically hindered substrates such as terminal alkenes; importantly, it prevents recombination and further isomerization of the internal ones.

Original languageAmerican English
Pages (from-to)5959-5965
Number of pages7
JournalChemCatChem
Volume12
Issue number23
DOIs
StatePublished - 4 Dec 2020

Bibliographical note

Publisher Copyright:
© 2020 Wiley-VCH GmbH

Keywords

  • alkenes
  • isomerization
  • ligand-metal cooperation
  • pincer complexes

Fingerprint

Dive into the research topics of 'Regioselective Isomerization of Terminal Alkenes Catalyzed by a PC(sp3)Pincer Complex with a Hemilabile Pendant Arm'. Together they form a unique fingerprint.

Cite this