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Nickel‐Catalyzed Anionic Cross‐Coupling Reaction of Lithium Sulfonimidoyl Alkylidene Carbenoids With Organolithiums
The mechanistic platform for a novel nickel(0)‐catalyzed anionic cross‐coupling reaction (ACCR) of lithium sulfonimidoyl alkylidene carbenoids (metalloalkenyl sulfoximines) with organometallic reagents is reported herein, affording substituted alkenylmetals and lithium sulfinamides. The Ni(0)‐cataly...
Autores principales: | , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
John Wiley and Sons Inc.
2020
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7079181/ https://www.ncbi.nlm.nih.gov/pubmed/31667889 http://dx.doi.org/10.1002/chem.201904862 |
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author | Erdelmeier, Irene Won, Joonghee Park, Steve Decker, Jürgen Bülow, Gerd Baik, Mu‐Hyun Gais, Hans‐Joachim |
author_facet | Erdelmeier, Irene Won, Joonghee Park, Steve Decker, Jürgen Bülow, Gerd Baik, Mu‐Hyun Gais, Hans‐Joachim |
author_sort | Erdelmeier, Irene |
collection | PubMed |
description | The mechanistic platform for a novel nickel(0)‐catalyzed anionic cross‐coupling reaction (ACCR) of lithium sulfonimidoyl alkylidene carbenoids (metalloalkenyl sulfoximines) with organometallic reagents is reported herein, affording substituted alkenylmetals and lithium sulfinamides. The Ni(0)‐catalyzed ACCR of three different types of metalloalkenyl sulfoximines, including acyclic, axially chiral and exocyclic derivatives, with sp(2) organolithiums and sp(2) and sp(3) Grignard reagents has been studied. The ACCR of metalloalkenyl sulfoximines with PhLi in the presence of the Ni(0)‐catalyst and precatalyst Ni(PPh(3))(2)Cl(2) afforded alkenyllithiums, under inversion of configuration at the C atom and complete retention at the S atom. In a combination of experimental and DFT studies, we propose a catalytic cycle of the Ni(0)‐catalyzed ACCR of lithioalkenyl sulfoximines. Computational studies reveal two distinctive pathways of the ACCR, depending on whether a phosphine or 1,5‐cyclooctadiene (COD) is the ligand of the Ni atom. They rectify the underlying importance of forming the key Ni(0)‐vinylidene intermediate through an indispensable electron‐rich Ni(0)‐center coordinated by phosphine ligands. Fundamentally, we present a mechanistic study in controlling the diastereoselectivity of the alkenyllithium formation via the key lithium sulfinamide coordinated Ni(0)‐vinylidene complex, which consequently avoids an unselective formation of an alkylidene carbene Ni‐complex and ultimately racemic alkenyllithium. |
format | Online Article Text |
id | pubmed-7079181 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | John Wiley and Sons Inc. |
record_format | MEDLINE/PubMed |
spelling | pubmed-70791812020-03-19 Nickel‐Catalyzed Anionic Cross‐Coupling Reaction of Lithium Sulfonimidoyl Alkylidene Carbenoids With Organolithiums Erdelmeier, Irene Won, Joonghee Park, Steve Decker, Jürgen Bülow, Gerd Baik, Mu‐Hyun Gais, Hans‐Joachim Chemistry Full Papers The mechanistic platform for a novel nickel(0)‐catalyzed anionic cross‐coupling reaction (ACCR) of lithium sulfonimidoyl alkylidene carbenoids (metalloalkenyl sulfoximines) with organometallic reagents is reported herein, affording substituted alkenylmetals and lithium sulfinamides. The Ni(0)‐catalyzed ACCR of three different types of metalloalkenyl sulfoximines, including acyclic, axially chiral and exocyclic derivatives, with sp(2) organolithiums and sp(2) and sp(3) Grignard reagents has been studied. The ACCR of metalloalkenyl sulfoximines with PhLi in the presence of the Ni(0)‐catalyst and precatalyst Ni(PPh(3))(2)Cl(2) afforded alkenyllithiums, under inversion of configuration at the C atom and complete retention at the S atom. In a combination of experimental and DFT studies, we propose a catalytic cycle of the Ni(0)‐catalyzed ACCR of lithioalkenyl sulfoximines. Computational studies reveal two distinctive pathways of the ACCR, depending on whether a phosphine or 1,5‐cyclooctadiene (COD) is the ligand of the Ni atom. They rectify the underlying importance of forming the key Ni(0)‐vinylidene intermediate through an indispensable electron‐rich Ni(0)‐center coordinated by phosphine ligands. Fundamentally, we present a mechanistic study in controlling the diastereoselectivity of the alkenyllithium formation via the key lithium sulfinamide coordinated Ni(0)‐vinylidene complex, which consequently avoids an unselective formation of an alkylidene carbene Ni‐complex and ultimately racemic alkenyllithium. John Wiley and Sons Inc. 2020-02-20 2020-03-02 /pmc/articles/PMC7079181/ /pubmed/31667889 http://dx.doi.org/10.1002/chem.201904862 Text en © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the http://creativecommons.org/licenses/by-nc-nd/4.0/ License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non‐commercial and no modifications or adaptations are made. |
spellingShingle | Full Papers Erdelmeier, Irene Won, Joonghee Park, Steve Decker, Jürgen Bülow, Gerd Baik, Mu‐Hyun Gais, Hans‐Joachim Nickel‐Catalyzed Anionic Cross‐Coupling Reaction of Lithium Sulfonimidoyl Alkylidene Carbenoids With Organolithiums |
title | Nickel‐Catalyzed Anionic Cross‐Coupling Reaction of Lithium Sulfonimidoyl Alkylidene Carbenoids With Organolithiums |
title_full | Nickel‐Catalyzed Anionic Cross‐Coupling Reaction of Lithium Sulfonimidoyl Alkylidene Carbenoids With Organolithiums |
title_fullStr | Nickel‐Catalyzed Anionic Cross‐Coupling Reaction of Lithium Sulfonimidoyl Alkylidene Carbenoids With Organolithiums |
title_full_unstemmed | Nickel‐Catalyzed Anionic Cross‐Coupling Reaction of Lithium Sulfonimidoyl Alkylidene Carbenoids With Organolithiums |
title_short | Nickel‐Catalyzed Anionic Cross‐Coupling Reaction of Lithium Sulfonimidoyl Alkylidene Carbenoids With Organolithiums |
title_sort | nickel‐catalyzed anionic cross‐coupling reaction of lithium sulfonimidoyl alkylidene carbenoids with organolithiums |
topic | Full Papers |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7079181/ https://www.ncbi.nlm.nih.gov/pubmed/31667889 http://dx.doi.org/10.1002/chem.201904862 |
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