Ring splitting of azetidin-2-ones via radical anions

The radical anions of azetidin-2-ones, generated by UV-irradiation in the presence of triethylamine, undergo ring-splitting via N-C4 or C3-C4 bond breaking, leading to open-chain amides. This reactivity diverges from that found for the neutral excited states, which is characterised by alpha-cleavage...

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Published inOrganic & biomolecular chemistry Vol. 10; no. 39; pp. 7928 - 7932
Main Authors Perez-Ruiz, Raul, Saez, Jose A., Domingo, Luis R., Consuelo Jimenez, M., Miranda, Miguel A.
Format Journal Article
LanguageEnglish
Published CAMBRIDGE Royal Soc Chemistry 21.10.2012
Subjects
Anions - chemistry
Azetidines - chemical synthesis
Azetidines - chemistry
Chemistry
Chemistry, Organic
Free Radicals - chemistry
Molecular Structure
Physical Sciences
Quantum Theory
Science & Technology
Ultraviolet Rays
ELECTRON
N-(ARYLIDENE(OR ALKYLIDENE)AMINO)-2-AZETIDINONES
MECHANISM
AMINES
BUILDING-BLOCKS
STEREOSELECTIVE-SYNTHESIS
MODEL
BETA-LACTAM RING
FRAGMENTATION
VINYL ETHERS
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Summary:The radical anions of azetidin-2-ones, generated by UV-irradiation in the presence of triethylamine, undergo ring-splitting via N-C4 or C3-C4 bond breaking, leading to open-chain amides. This reactivity diverges from that found for the neutral excited states, which is characterised by alpha-cleavage. The preference for beta-cleavage is supported by DFT theoretical calculations on the energy barriers associated with the involved transition states. Thus, injection of one electron into the azetidin-2-one moiety constitutes a complementary activation strategy which may be exploited to produce new chemistry.
Bibliography:ObjectType-Article-1
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ISSN:1477-0520
1477-0539
DOI:10.1039/c2ob26528a