Atom and step economical synthesis of acyclic quaternary centers via iridium-catalyzed hydroarylative cross-coupling of 1,1-disubstituted alkenes

Phillippa Cooper, Andrew G. Dalling, Elliot H. E. Farrar, Timothy P. Aldhous, Simon Grélaud, Eleanor Lester, Lyman J. Feron, Paul D. Kemmitt, Matthew N. Grayson, John F. Bower

Research output: Contribution to journalArticlepeer-review

Abstract

Quaternary benzylic centers are accessed with high atom and step economy by Ir-catalyzed alkene hydroarylation. These studies provide unique examples of the use of non-polarized 1,1-disubstituted alkenes in branch selective Murai-type hydro(hetero)arylations. Detailed mechanistic studies have been undertaken, and these indicate that the first irreversible step is the demanding alkene carbometallation process. Structure-reactivity studies show that the efficiency of this is critically dependent on key structural features of the ligand. Computational studies have been undertaken to rationalize this experimental data, showing how more sterically demanding ligands reduce the reaction barrier via predistortion of the reacting intermediate. The key insight disclosed here will underpin the ongoing development of increasingly sophisticated branch selective Murai hydroarylations.
Original languageEnglish
Pages (from-to)11183-11189
Number of pages7
JournalChemical Science
Volume13
Issue number37
Early online date13 Sep 2022
DOIs
Publication statusPublished - 7 Oct 2022

ASJC Scopus subject areas

  • Chemistry(all)

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