Hydroarylation of oleﬁns catalysed by a dimeric ytterbium(II) alkyl

Georgia Richardson; Iskander Douair; Scott Cameron; Joe Bracegirdle; Robert Keyzers; Michael Hill; Laurent Maron; Mathew Anker

doi:10.1038/s41467-021-23444-x

Hydroarylation of oleﬁns catalysed by a dimeric ytterbium(II) alkyl

Georgia Richardson, Iskander Douair, Scott Cameron, Joe Bracegirdle, Robert Keyzers, Michael Hill, Laurent Maron, Mathew Anker

Research output: Contribution to journal › Article › peer-review

22 Citations (SciVal)

Abstract

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.

Original language	English
Article number	3147
Number of pages	7
Journal	Nature Communications
Volume	12
Issue number	1
DOIs	https://doi.org/10.1038/s41467-021-23444-x
Publication status	Published - 25 May 2021

Bibliographical note

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.

ASJC Scopus subject areas

General Physics and Astronomy
General Chemistry
General Biochemistry,Genetics and Molecular Biology

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10.1038/s41467-021-23444-xLicence: CC BY

Cite this

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title = "Hydroarylation of oleﬁns catalysed by a dimeric ytterbium(II) alkyl",

abstract = "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.",

author = "Georgia Richardson and Iskander Douair and Scott Cameron and Joe Bracegirdle and Robert Keyzers and Michael Hill and Laurent Maron and Mathew Anker",

note = "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.",

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AU - Keyzers, Robert

AU - Hill, Michael

AU - Maron, Laurent

AU - Anker, Mathew

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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.

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Hydroarylation of oleﬁns catalysed by a dimeric ytterbium(II) alkyl

Abstract

Bibliographical note

ASJC Scopus subject areas

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CCDC 2032029: Experimental Crystal Structure Determination

CCDC 2032031: Experimental Crystal Structure Determination

CCDC 2032030: Experimental Crystal Structure Determination

Cite this

Hydroarylation of oleﬁns catalysed by a dimeric ytterbium(II) alkyl

Abstract

Bibliographical note

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Datasets

CCDC 2032029: Experimental Crystal Structure Determination

CCDC 2032031: Experimental Crystal Structure Determination

CCDC 2032030: Experimental Crystal Structure Determination

Cite this