Cooper, Phillippa, Dalling, Andrew G, Farrar, Elliot HE, Aldhous, Timothy P 
ORCID: 0000-0003-2031-7454, Grelaud, Simon, Lester, Eleanor, Feron, Lyman J, Kemmitt, Paul D, Grayson, Matthew N and Bower, John F ORCID: 0000-0002-7551-8221
(2022)
Atom and step economical synthesis of acyclic quaternary centers <i>via</i> iridium-catalyzed hydroarylative cross-coupling of 1,1-disubstituted alkenes.
CHEMICAL SCIENCE, 13 (37).
pp. 11183-11189.
|
PDF
Atom and step economical synthesis of acyclic quaternary centers iviai iridium-catalyzed hydroarylative cross-coupling of 1,.pdf - Published version Download (2MB) | Preview |
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 <i>via</i> predistortion of the reacting intermediate. The key insight disclosed here will underpin the ongoing development of increasingly sophisticated branch selective Murai hydroarylations.
| Item Type: | Article |
|---|---|
| Depositing User: | Symplectic Admin |
| Date Deposited: | 21 Nov 2022 16:47 |
| Last Modified: | 07 Oct 2023 02:28 |
| DOI: | 10.1039/d2sc02790a |
| Open Access URL: | https://doi.org/10.1039/D2SC02790A |
| Related URLs: | |
| URI: | https://livrepository.liverpool.ac.uk/id/eprint/3166308 |
Dimensions
Dimensions
