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

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. © 2020 Wiley-VCH GmbH

Authors
De-Botton S.1 , Filippov D.O.A.2 , Shubina E.S. 2 , Belkova N.V.2 , Gelman D. 1, 3
Journal
Publisher
Wiley Blackwell
Language
English
Status
Published
Year
2020
Organizations
  • 1 Institute of Chemistry, Edmond J. Safra Campus, The Hebrew University of Jerusalem, Jerusalem, 91904, Israel
  • 2 A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Street 28, Moscow, 119991, Russian Federation
  • 3 Peoples' Friendship University of Russia (RUDN University), Miklukho-Maklay St., 6, Moscow, 117198, Russian Federation
Keywords
alkenes; isomerization; ligand-metal cooperation; pincer complexes
Date of creation
02.11.2020
Date of change
02.11.2020
Short link
https://repository.rudn.ru/en/records/article/record/65460/
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