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Stoichiometric Photochemical Carbene Transfer by Bamford–Stevens Reaction

The photolysis of diazoalkanes is a timely strategy to conduct carbene‐transfer reactions under mild and metal‐free reaction conditions, and has developed as an important alternative to conventional metal‐catalyzed carbene‐transfer reactions. One of the major limitations lies within the rapidly occu...

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Autores principales: Jana, Sripati, Li, Fang, Empel, Claire, Verspeek, Dennis, Aseeva, Polina, Koenigs, Rene M.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2020
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7065054/
https://www.ncbi.nlm.nih.gov/pubmed/31825123
http://dx.doi.org/10.1002/chem.201904994
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author Jana, Sripati
Li, Fang
Empel, Claire
Verspeek, Dennis
Aseeva, Polina
Koenigs, Rene M.
author_facet Jana, Sripati
Li, Fang
Empel, Claire
Verspeek, Dennis
Aseeva, Polina
Koenigs, Rene M.
author_sort Jana, Sripati
collection PubMed
description The photolysis of diazoalkanes is a timely strategy to conduct carbene‐transfer reactions under mild and metal‐free reaction conditions, and has developed as an important alternative to conventional metal‐catalyzed carbene‐transfer reactions. One of the major limitations lies within the rapidly occurring side reaction of the carbene intermediate with remaining diazoalkane molecules that result in the use of an excess of the reaction partner and thus impacts on the reaction efficiency. Herein, we describe a protocol that takes advantage of the in situ generation of donor–acceptor diazoalkanes by Bamford–Stevens reaction. Following this strategy, the concentration of the diazoalkane reaction partner can be minimized to reduce unwanted side reactions and to now conduct photochemical carbene transfer reactions under stoichiometric reaction conditions. We have explored this approach in the C−H and N−H functionalization and cyclopropanation reaction of N‐heterocycles and could demonstrate the applicability of this method in 51 examples.
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spelling pubmed-70650542020-03-16 Stoichiometric Photochemical Carbene Transfer by Bamford–Stevens Reaction Jana, Sripati Li, Fang Empel, Claire Verspeek, Dennis Aseeva, Polina Koenigs, Rene M. Chemistry Communications The photolysis of diazoalkanes is a timely strategy to conduct carbene‐transfer reactions under mild and metal‐free reaction conditions, and has developed as an important alternative to conventional metal‐catalyzed carbene‐transfer reactions. One of the major limitations lies within the rapidly occurring side reaction of the carbene intermediate with remaining diazoalkane molecules that result in the use of an excess of the reaction partner and thus impacts on the reaction efficiency. Herein, we describe a protocol that takes advantage of the in situ generation of donor–acceptor diazoalkanes by Bamford–Stevens reaction. Following this strategy, the concentration of the diazoalkane reaction partner can be minimized to reduce unwanted side reactions and to now conduct photochemical carbene transfer reactions under stoichiometric reaction conditions. We have explored this approach in the C−H and N−H functionalization and cyclopropanation reaction of N‐heterocycles and could demonstrate the applicability of this method in 51 examples. John Wiley and Sons Inc. 2020-02-21 2020-02-26 /pmc/articles/PMC7065054/ /pubmed/31825123 http://dx.doi.org/10.1002/chem.201904994 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/4.0/ License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes.
spellingShingle Communications
Jana, Sripati
Li, Fang
Empel, Claire
Verspeek, Dennis
Aseeva, Polina
Koenigs, Rene M.
Stoichiometric Photochemical Carbene Transfer by Bamford–Stevens Reaction
title Stoichiometric Photochemical Carbene Transfer by Bamford–Stevens Reaction
title_full Stoichiometric Photochemical Carbene Transfer by Bamford–Stevens Reaction
title_fullStr Stoichiometric Photochemical Carbene Transfer by Bamford–Stevens Reaction
title_full_unstemmed Stoichiometric Photochemical Carbene Transfer by Bamford–Stevens Reaction
title_short Stoichiometric Photochemical Carbene Transfer by Bamford–Stevens Reaction
title_sort stoichiometric photochemical carbene transfer by bamford–stevens reaction
topic Communications
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7065054/
https://www.ncbi.nlm.nih.gov/pubmed/31825123
http://dx.doi.org/10.1002/chem.201904994
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