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

Lookup NU author(s): Nathan Davison, Dr Paul Waddell, Dr Corinne Wills, Dr Casey Dixon, Dr Erli Lu

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This work is licensed under a Creative Commons Attribution 4.0 International License (CC BY 4.0).


Abstract

© 2023 The Authors. Published by American Chemical Society.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(CH2SiMe3)(Me6Tren)] (1-Na) (Me6Tren: tris[2-(dimethylamino)ethyl]amine) stabilized by a tetra-dentate neutral amine ligand Me6Tren. Employing organo-carbonyl substrates (ketones, aldehydes, amides, ester), we demonstrated that 1-Na features distinct reactivity patterns compared with its lithium counterpart, [Li(CH2SiMe3)(Me6Tren)] (1-Li). Based on this knowledge, we further developed a ligand-catalysis strategy to conduct ketone/aldehyde methylenations, using [NaCH2SiMe3]∞ as the CH2 feedstock, replacing the widely used but hazardous/expensive C═O methylenation methods, such as Wittig, Tebbe, Julia/Julia-Kocieński, Peterson, and so on.


Publication metadata

Author(s): Davison N, McMullin CL, Zhang L, Hu S-X, Waddell PG, Wills C, Dixon C, Lu E

Publication type: Article

Publication status: Published

Journal: Journal of the American Chemical Society

Year: 2023

Volume: 145

Issue: 11

Pages: 6562–6576

Print publication date: 22/03/2023

Online publication date: 08/03/2023

Acceptance date: 30/01/2023

Date deposited: 28/03/2023

ISSN (print): 0002-7863

ISSN (electronic): 1520-5126

Publisher: American Chemical Society

URL: https://doi.org/10.1021/jacs.3c01033

DOI: 10.1021/jacs.3c01033

PubMed id: 36890641


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Funding

Funder referenceFunder name
21976014
E20-5153
E22-3348740748
EPSRC North East Centre of Energy Materials (NECEM)
Newcastle University Academic Track (NUAcT) Fellowship Scheme
U1930402

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