Stoichiometric Photochemical Carbene Transfer by Bamford–Stevens Reaction
| Autor: | Rene M. Koenigs, Polina Aseeva, Sripati Jana, Dennis Verspeek, Fang Li, Claire Empel |
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| Rok vydání: | 2020 |
| Předmět: |
Cyclopropanation
Side reaction cyclopropanation 010402 general chemistry Photochemistry 01 natural sciences Catalysis N−H functionalization C−H functionalization chemistry.chemical_compound Molecule Photochemistry | Hot Paper Reaction conditions photochemistry 010405 organic chemistry Communication Organic Chemistry Photodissociation General Chemistry Communications 0104 chemical sciences carbenes chemistry Bamford–Stevens reaction ddc:540 Carbene Stoichiometry |
| Zdroj: | Chemistry (Weinheim an Der Bergstrasse, Germany) Chemistry-a European journal 26(12), 2586-2591 (2020). doi:10.1002/chem.201904994 |
| ISSN: | 1521-3765 0947-6539 |
| DOI: | 10.1002/chem.201904994 |
| Popis: | 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. Cyclopropanation: Bamford–Stevens reactions in the presence of blue light open up a pathway to overcome typical limitations of photochemical carbene‐transfer reactions. Following this methodology, the C−H functionalization of indole heterocycles can be performed in high efficiency under stoichiometric conditions (see scheme). |
| Databáze: | OpenAIRE |
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