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Towards Substrate–Reagent Interaction of Lochmann–Schlosser Bases in THF: Bridging THF Hides Potential Reaction Site of a Chiral Superbase

The metalation of N,N‐dimethylaminomethylferrocene in THF by the superbasic mixture of ( n )BuLi/KO( t )Bu proceeds readily at low temperatures to afford a bimetallic Li(2)K(2) aggregate containing ferrocenyl anions and tert‐butoxide. Starting from an enantiomerically enriched ortho‐lithiated aminom...

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Autores principales: Brieger, Lukas, Schrimpf, Tobias, Scheel, Rebecca, Unkelbach, Christian, Strohmann, Carsten
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10092790/
https://www.ncbi.nlm.nih.gov/pubmed/36098179
http://dx.doi.org/10.1002/chem.202202660
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author Brieger, Lukas
Schrimpf, Tobias
Scheel, Rebecca
Unkelbach, Christian
Strohmann, Carsten
author_facet Brieger, Lukas
Schrimpf, Tobias
Scheel, Rebecca
Unkelbach, Christian
Strohmann, Carsten
author_sort Brieger, Lukas
collection PubMed
description The metalation of N,N‐dimethylaminomethylferrocene in THF by the superbasic mixture of ( n )BuLi/KO( t )Bu proceeds readily at low temperatures to afford a bimetallic Li(2)K(2) aggregate containing ferrocenyl anions and tert‐butoxide. Starting from an enantiomerically enriched ortho‐lithiated aminomethylferrocene, an enantiomerically pure superbase can be prepared. The molecular compound exhibits superbasic behavior deprotonating N,N‐dimethylbenzylamine in the α‐position and is also capable of deprotonating toluene. Quantum chemical calculations provide insight into the role of the bridging THF molecule to the possible substrate–reagent interaction. In addition, a benzylpotassium alkoxide adduct gives a closer look into the corresponding reaction site of the Lochmann–Schlosser base that is reported herein.
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spelling pubmed-100927902023-04-13 Towards Substrate–Reagent Interaction of Lochmann–Schlosser Bases in THF: Bridging THF Hides Potential Reaction Site of a Chiral Superbase Brieger, Lukas Schrimpf, Tobias Scheel, Rebecca Unkelbach, Christian Strohmann, Carsten Chemistry Research Articles The metalation of N,N‐dimethylaminomethylferrocene in THF by the superbasic mixture of ( n )BuLi/KO( t )Bu proceeds readily at low temperatures to afford a bimetallic Li(2)K(2) aggregate containing ferrocenyl anions and tert‐butoxide. Starting from an enantiomerically enriched ortho‐lithiated aminomethylferrocene, an enantiomerically pure superbase can be prepared. The molecular compound exhibits superbasic behavior deprotonating N,N‐dimethylbenzylamine in the α‐position and is also capable of deprotonating toluene. Quantum chemical calculations provide insight into the role of the bridging THF molecule to the possible substrate–reagent interaction. In addition, a benzylpotassium alkoxide adduct gives a closer look into the corresponding reaction site of the Lochmann–Schlosser base that is reported herein. John Wiley and Sons Inc. 2022-10-17 2022-12-09 /pmc/articles/PMC10092790/ /pubmed/36098179 http://dx.doi.org/10.1002/chem.202202660 Text en © 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH https://creativecommons.org/licenses/by/4.0/This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
spellingShingle Research Articles
Brieger, Lukas
Schrimpf, Tobias
Scheel, Rebecca
Unkelbach, Christian
Strohmann, Carsten
Towards Substrate–Reagent Interaction of Lochmann–Schlosser Bases in THF: Bridging THF Hides Potential Reaction Site of a Chiral Superbase
title Towards Substrate–Reagent Interaction of Lochmann–Schlosser Bases in THF: Bridging THF Hides Potential Reaction Site of a Chiral Superbase
title_full Towards Substrate–Reagent Interaction of Lochmann–Schlosser Bases in THF: Bridging THF Hides Potential Reaction Site of a Chiral Superbase
title_fullStr Towards Substrate–Reagent Interaction of Lochmann–Schlosser Bases in THF: Bridging THF Hides Potential Reaction Site of a Chiral Superbase
title_full_unstemmed Towards Substrate–Reagent Interaction of Lochmann–Schlosser Bases in THF: Bridging THF Hides Potential Reaction Site of a Chiral Superbase
title_short Towards Substrate–Reagent Interaction of Lochmann–Schlosser Bases in THF: Bridging THF Hides Potential Reaction Site of a Chiral Superbase
title_sort towards substrate–reagent interaction of lochmann–schlosser bases in thf: bridging thf hides potential reaction site of a chiral superbase
topic Research Articles
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10092790/
https://www.ncbi.nlm.nih.gov/pubmed/36098179
http://dx.doi.org/10.1002/chem.202202660
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