TY - JOUR
T1 - Hydroarylation of olefins catalysed by a dimeric ytterbium(II) alkyl
AU - Richardson, Georgia
AU - Douair, Iskander
AU - Cameron, Scott
AU - Bracegirdle, Joe
AU - Keyzers, Robert
AU - Hill, Michael
AU - Maron, Laurent
AU - Anker, Mathew
N1 - Funding Information:
We thank the AINSE Early Career Research Grant, Victoria University of Wellington, University Research Fund (M.D.A), AINSE Honours Scholarship, Curtis-Gordon Research Scholarship, Dr. Margaret L. Bailey Award and Victoria University of Wellington Doctoral Scholarship (G.M.R) for financial support for this work. L.M. is a senior member of the Institut Universitaire de France. CalMip is acknowledged for a generous grant of computing time.
Data Availability
Crystallographic data for the structures reported in this Article have been deposited at the Cambridge Crystallographic Data Centre under deposition numbers: CCDC 2032031 (1), 2032028 (2), 2032030 (3), 2032029 (4), and 2034334 (6). These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif. All data supporting the findings of this study are available within the article, as well as the Supplementary Information file, or available from the corresponding authors on request.
PY - 2021/5/25
Y1 - 2021/5/25
N2 - Although the nucleophilic alkylation of aromatics has recently been achieved with a variety of potent main group reagents, all of this reactivity is limited to a stoichiometric regime. We now report that the ytterbium(II) hydride, [BDIDippYbH]2 (BDIDipp = CH[C(CH3)NDipp]2, Dipp = 2,6-diisopropylphenyl), reacts with ethene and propene to provide the ytterbium(II) n-alkyls, [BDIDippYbR]2 (R = Et or Pr), both of which alkylate benzene at room temperature. Density functional theory (DFT) calculations indicate that this latter process operates through the nucleophilic (SN2) displacement of hydride, while the resultant regeneration of [BDIDippYbH]2 facilitates further reaction with ethene or propene and enables the direct catalytic (anti-Markovnikov) hydroarylation of both alkenes with a benzene C-H bond.
AB - Although the nucleophilic alkylation of aromatics has recently been achieved with a variety of potent main group reagents, all of this reactivity is limited to a stoichiometric regime. We now report that the ytterbium(II) hydride, [BDIDippYbH]2 (BDIDipp = CH[C(CH3)NDipp]2, Dipp = 2,6-diisopropylphenyl), reacts with ethene and propene to provide the ytterbium(II) n-alkyls, [BDIDippYbR]2 (R = Et or Pr), both of which alkylate benzene at room temperature. Density functional theory (DFT) calculations indicate that this latter process operates through the nucleophilic (SN2) displacement of hydride, while the resultant regeneration of [BDIDippYbH]2 facilitates further reaction with ethene or propene and enables the direct catalytic (anti-Markovnikov) hydroarylation of both alkenes with a benzene C-H bond.
UR - http://www.scopus.com/inward/record.url?scp=85106944402&partnerID=8YFLogxK
U2 - 10.1038/s41467-021-23444-x
DO - 10.1038/s41467-021-23444-x
M3 - Article
SN - 2041-1723
VL - 12
JO - Nature Communications
JF - Nature Communications
IS - 1
M1 - 3147
ER -