Li vs Na: Divergent Reaction Patterns between Organolithium and Organosodium Complexes and Ligand-Catalyzed Ketone/Aldehyde Methylenation

Nathan Davison; Claire L. McMullin; Lu Zhang; Shu-Xian Hu; Paul G. Waddell; Corrine Wills; Casey Dixon; Erli Lu

doi:10.1021/jacs.3c01033

Li vs Na: Divergent Reaction Patterns between Organolithium and Organosodium Complexes and Ligand-Catalyzed Ketone/Aldehyde Methylenation

Nathan Davison, Claire L. McMullin, Lu Zhang, Shu-Xian Hu, Paul G. Waddell, Corrine Wills, Casey Dixon, Erli Lu

Department of Chemistry

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

19 Citations (SciVal)

Abstract

Organosodium chemistry is underdeveloped compared with organolithium chemistry, and all the reported organosodium complexes exhibit similar, if not identical, reactivity patterns to their lithium counterparts. Herein, we report a rare organosodium monomeric complex, namely, [Na(CH ₂SiMe ₃)(Me ₆Tren)] (1-Na) (Me ₆Tren: tris[2-(dimethylamino)ethyl]amine) stabilized by a tetra-dentate neutral amine ligand Me ₆Tren. Employing organo-carbonyl substrates (ketones, aldehydes, amides, ester), we demonstrated that 1-Na features distinct reactivity patterns compared with its lithium counterpart, [Li(CH ₂SiMe ₃)(Me ₆Tren)] (1-Li). Based on this knowledge, we further developed a ligand-catalysis strategy to conduct ketone/aldehyde methylenations, using [NaCH ₂SiMe ₃] _∞ as the CH ₂ feedstock, replacing the widely used but hazardous/expensive C═O methylenation methods, such as Wittig, Tebbe, Julia/Julia-Kocieński, Peterson, and so on.

Original language	English
Pages (from-to)	6562-6576
Number of pages	15
Journal	Journal of the American Chemical Society
Volume	145
Issue number	11
Early online date	8 Mar 2023
DOIs	https://doi.org/10.1021/jacs.3c01033
Publication status	Published - 22 Mar 2023

Bibliographical note

Funding Information:
E.L. thanks the Newcastle University Academic Track (NUAcT) Fellowship Scheme, EPSRC North East Centre of Energy Materials (NECEM) and the Royal Society of Chemistry Research Enablement Grants (E20-5153) for financial support. N.D. thanks Newcastle University for a NUAcT PhD studentship and the Royal Society of Chemistry Research Enablement Grants (E22-3348740748). C.L.M. thanks the University of Bath for access to Anatra High Performance Computing Service. S.-X.H. acknowledges the financial support from the National Natural Science Foundation of China (Nos. 21976014 and U1930402) and the generous grants of computer time from Tianhe2-JK.

AccessionCodes
CCDC2217099(1-Na),2217100([NaCH2SiMe3]∞), 2217101(5),2217102(3-Na)and2238438(6)contain the supplementary crystallographic data for the corresponding complexes.These data can be obtained free of charge via www. ccdc.cam.ac.uk/data_request/cif, or by emailing data_ [email protected], or by contacting The Cambridge Crystallographic DataCentre,12 Union Road, Cambridge CB21EZ,UK;fax:+441223336033.

Funding Information:
This article is dedicated to Professor Robert E. Mulvey, University of Strathclyde, for his pioneering contribution in Group-1 metal chemistry. The authors thank the Newcastle University Chemistry Technical Support Team (Dr. Laura McCorkindale, Dr. Amy Roberts and Mr. Niall Straughan) for supporting our research. E.L. thanks Drs. Keith Izod, Roly Armstrong, and Matthew Hopkinson (all at Newcastle University) for insightful discussions. The authors thank Professor Eva Hevia (Universität Bern) for providing in-depth insight of the recent publication(50) regarding 1-Na from her group. E.L. thanks the Newcastle University Academic Track (NUAcT) Fellowship Scheme, EPSRC North East Centre of Energy Materials (NECEM) and the Royal Society of Chemistry Research Enablement Grants (E20-5153) for financial support. N.D. thanks Newcastle University for a NUAcT PhD studentship and the Royal Society of Chemistry Research Enablement Grants (E22-3348740748). C.L.M. thanks the University of Bath for access to Anatra High Performance Computing Service. S.-X.H. acknowledges the financial support from the National Natural Science Foundation of China (Nos. 21976014 and U1930402) and the generous grants of computer time from Tianhe2-JK.

Publisher Copyright:
© 2023 The Authors. Published by American Chemical Society.

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10.1021/jacs.3c01033Licence: CC BY

Cite this

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title = "Li vs Na: Divergent Reaction Patterns between Organolithium and Organosodium Complexes and Ligand-Catalyzed Ketone/Aldehyde Methylenation",

abstract = "Organosodium chemistry is underdeveloped compared with organolithium chemistry, and all the reported organosodium complexes exhibit similar, if not identical, reactivity patterns to their lithium counterparts. Herein, we report a rare organosodium monomeric complex, namely, [Na(CH 2SiMe 3)(Me 6Tren)] (1-Na) (Me 6Tren: tris[2-(dimethylamino)ethyl]amine) stabilized by a tetra-dentate neutral amine ligand Me 6Tren. Employing organo-carbonyl substrates (ketones, aldehydes, amides, ester), we demonstrated that 1-Na features distinct reactivity patterns compared with its lithium counterpart, [Li(CH 2SiMe 3)(Me 6Tren)] (1-Li). Based on this knowledge, we further developed a ligand-catalysis strategy to conduct ketone/aldehyde methylenations, using [NaCH 2SiMe 3] ∞ as the CH 2 feedstock, replacing the widely used but hazardous/expensive C═O methylenation methods, such as Wittig, Tebbe, Julia/Julia-Kocie{\'n}ski, Peterson, and so on.",

author = "Nathan Davison and McMullin, {Claire L.} and Lu Zhang and Shu-Xian Hu and Waddell, {Paul G.} and Corrine Wills and Casey Dixon and Erli Lu",

note = "Funding Information: E.L. thanks the Newcastle University Academic Track (NUAcT) Fellowship Scheme, EPSRC North East Centre of Energy Materials (NECEM) and the Royal Society of Chemistry Research Enablement Grants (E20-5153) for financial support. N.D. thanks Newcastle University for a NUAcT PhD studentship and the Royal Society of Chemistry Research Enablement Grants (E22-3348740748). C.L.M. thanks the University of Bath for access to Anatra High Performance Computing Service. S.-X.H. acknowledges the financial support from the National Natural Science Foundation of China (Nos. 21976014 and U1930402) and the generous grants of computer time from Tianhe2-JK. AccessionCodes CCDC2217099(1-Na),2217100([NaCH2SiMe3]∞), 2217101(5),2217102(3-Na)and2238438(6)contain the supplementary crystallographic data for the corresponding complexes.These data can be obtained free of charge via www. ccdc.cam.ac.uk/data_request/cif, or by emailing data_ [email protected], or by contacting The Cambridge Crystallographic DataCentre,12 Union Road, Cambridge CB21EZ,UK;fax:+441223336033. Funding Information: This article is dedicated to Professor Robert E. Mulvey, University of Strathclyde, for his pioneering contribution in Group-1 metal chemistry. The authors thank the Newcastle University Chemistry Technical Support Team (Dr. Laura McCorkindale, Dr. Amy Roberts and Mr. Niall Straughan) for supporting our research. E.L. thanks Drs. Keith Izod, Roly Armstrong, and Matthew Hopkinson (all at Newcastle University) for insightful discussions. The authors thank Professor Eva Hevia (Universit{\"a}t Bern) for providing in-depth insight of the recent publication(50) regarding 1-Na from her group. E.L. thanks the Newcastle University Academic Track (NUAcT) Fellowship Scheme, EPSRC North East Centre of Energy Materials (NECEM) and the Royal Society of Chemistry Research Enablement Grants (E20-5153) for financial support. N.D. thanks Newcastle University for a NUAcT PhD studentship and the Royal Society of Chemistry Research Enablement Grants (E22-3348740748). C.L.M. thanks the University of Bath for access to Anatra High Performance Computing Service. S.-X.H. acknowledges the financial support from the National Natural Science Foundation of China (Nos. 21976014 and U1930402) and the generous grants of computer time from Tianhe2-JK. Publisher Copyright: {\textcopyright} 2023 The Authors. Published by American Chemical Society.",

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doi = "10.1021/jacs.3c01033",

language = "English",

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T1 - Li vs Na: Divergent Reaction Patterns between Organolithium and Organosodium Complexes and Ligand-Catalyzed Ketone/Aldehyde Methylenation

AU - Davison, Nathan

AU - McMullin, Claire L.

AU - Zhang, Lu

AU - Hu, Shu-Xian

AU - Waddell, Paul G.

AU - Wills, Corrine

AU - Dixon, Casey

AU - Lu, Erli

N1 - Funding Information: E.L. thanks the Newcastle University Academic Track (NUAcT) Fellowship Scheme, EPSRC North East Centre of Energy Materials (NECEM) and the Royal Society of Chemistry Research Enablement Grants (E20-5153) for financial support. N.D. thanks Newcastle University for a NUAcT PhD studentship and the Royal Society of Chemistry Research Enablement Grants (E22-3348740748). C.L.M. thanks the University of Bath for access to Anatra High Performance Computing Service. S.-X.H. acknowledges the financial support from the National Natural Science Foundation of China (Nos. 21976014 and U1930402) and the generous grants of computer time from Tianhe2-JK. AccessionCodes CCDC2217099(1-Na),2217100([NaCH2SiMe3]∞), 2217101(5),2217102(3-Na)and2238438(6)contain the supplementary crystallographic data for the corresponding complexes.These data can be obtained free of charge via www. ccdc.cam.ac.uk/data_request/cif, or by emailing data_ [email protected], or by contacting The Cambridge Crystallographic DataCentre,12 Union Road, Cambridge CB21EZ,UK;fax:+441223336033. Funding Information: This article is dedicated to Professor Robert E. Mulvey, University of Strathclyde, for his pioneering contribution in Group-1 metal chemistry. The authors thank the Newcastle University Chemistry Technical Support Team (Dr. Laura McCorkindale, Dr. Amy Roberts and Mr. Niall Straughan) for supporting our research. E.L. thanks Drs. Keith Izod, Roly Armstrong, and Matthew Hopkinson (all at Newcastle University) for insightful discussions. The authors thank Professor Eva Hevia (Universität Bern) for providing in-depth insight of the recent publication(50) regarding 1-Na from her group. E.L. thanks the Newcastle University Academic Track (NUAcT) Fellowship Scheme, EPSRC North East Centre of Energy Materials (NECEM) and the Royal Society of Chemistry Research Enablement Grants (E20-5153) for financial support. N.D. thanks Newcastle University for a NUAcT PhD studentship and the Royal Society of Chemistry Research Enablement Grants (E22-3348740748). C.L.M. thanks the University of Bath for access to Anatra High Performance Computing Service. S.-X.H. acknowledges the financial support from the National Natural Science Foundation of China (Nos. 21976014 and U1930402) and the generous grants of computer time from Tianhe2-JK. Publisher Copyright: © 2023 The Authors. Published by American Chemical Society.

PY - 2023/3/22

Y1 - 2023/3/22

N2 - Organosodium chemistry is underdeveloped compared with organolithium chemistry, and all the reported organosodium complexes exhibit similar, if not identical, reactivity patterns to their lithium counterparts. Herein, we report a rare organosodium monomeric complex, namely, [Na(CH 2SiMe 3)(Me 6Tren)] (1-Na) (Me 6Tren: tris[2-(dimethylamino)ethyl]amine) stabilized by a tetra-dentate neutral amine ligand Me 6Tren. Employing organo-carbonyl substrates (ketones, aldehydes, amides, ester), we demonstrated that 1-Na features distinct reactivity patterns compared with its lithium counterpart, [Li(CH 2SiMe 3)(Me 6Tren)] (1-Li). Based on this knowledge, we further developed a ligand-catalysis strategy to conduct ketone/aldehyde methylenations, using [NaCH 2SiMe 3] ∞ as the CH 2 feedstock, replacing the widely used but hazardous/expensive C═O methylenation methods, such as Wittig, Tebbe, Julia/Julia-Kocieński, Peterson, and so on.

AB - Organosodium chemistry is underdeveloped compared with organolithium chemistry, and all the reported organosodium complexes exhibit similar, if not identical, reactivity patterns to their lithium counterparts. Herein, we report a rare organosodium monomeric complex, namely, [Na(CH 2SiMe 3)(Me 6Tren)] (1-Na) (Me 6Tren: tris[2-(dimethylamino)ethyl]amine) stabilized by a tetra-dentate neutral amine ligand Me 6Tren. Employing organo-carbonyl substrates (ketones, aldehydes, amides, ester), we demonstrated that 1-Na features distinct reactivity patterns compared with its lithium counterpart, [Li(CH 2SiMe 3)(Me 6Tren)] (1-Li). Based on this knowledge, we further developed a ligand-catalysis strategy to conduct ketone/aldehyde methylenations, using [NaCH 2SiMe 3] ∞ as the CH 2 feedstock, replacing the widely used but hazardous/expensive C═O methylenation methods, such as Wittig, Tebbe, Julia/Julia-Kocieński, Peterson, and so on.

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Li vs Na: Divergent Reaction Patterns between Organolithium and Organosodium Complexes and Ligand-Catalyzed Ketone/Aldehyde Methylenation

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Li vs Na: Divergent Reaction Patterns between Organolithium and Organosodium Complexes and Ligand-Catalyzed Ketone/Aldehyde Methylenation

Abstract

Bibliographical note

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