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Stoichiometric Photochemical Carbene Transfer by Bamford–Stevens Reaction
- Source :
- Chemistry (Weinheim an Der Bergstrasse, Germany), Chemistry-a European journal 26(12), 2586-2591 (2020). doi:10.1002/chem.201904994
- Publication Year :
- 2020
- Publisher :
- Wiley, 2020.
-
Abstract
- 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.<br />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).
- Subjects :
- 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
Subjects
Details
- ISSN :
- 15213765 and 09476539
- Volume :
- 26
- Database :
- OpenAIRE
- Journal :
- Chemistry – A European Journal
- Accession number :
- edsair.doi.dedup.....998a246dc848355190d4a7e07cfada39