Fluorine-Enabled Photochemical Generation of Carbonyl Ylide 1,3-Dipoles
- 1Department Chemie, Johannes Gutenberg-Universität, Duesbergweg 10-14, Mainz, Germany, 55128
- 2Instituto de Investigación Química de la Universidad de La Rioja (IQUR), Universidad de La Rioja Madre de Dios
Abstract
The photochemistry of carbonyl compounds underpins a wide range of modern synthetic transformations. However, photoinduced rearrangements, despite their unique potential for skeletal reorganization, remain conspicuously underexplored. Here, we show that fluorine can be used as a design principle to divert these reactions from established photochemical pathways. Mechanistic investigations combining experimental, spectroscopic and computational approaches support an unusual singlet excited state pathway involving initial cyclization followed by skeletal rearrangement. This sequence enables the formation of carbonyl ylide 1,3-dipoles, while exhibiting a pronounced increase in polarization along the reaction path. The high efficiency and selectivity of the process provide an attractive platform for isomerization and photoclick chemistry, while its compatibility with water and oxygen broadens the potential for bioorthogonal applications.
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BibTeX
@misc{pedada2026fluorineenabled,
title = {{Fluorine-Enabled Photochemical Generation of Carbonyl Ylide 1,3-Dipoles}},
author = {Abhilash Pedada and Jérémy Pecourneau and Alejandro García-Eguizábal and Daniil Tkatchev and Raúl Losantos and Christoph Kerzig and Ignacio Funes-Ardoiz and Johannes M. Wahl},
howpublished = {ChemRxiv},
year = {2026},
month = sep,
doi = {10.26434/chemrxiv.15008235/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008235/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Fluorine-Enabled Photochemical Generation of Carbonyl Ylide 1,3-Dipoles
AU - Abhilash Pedada
AU - Jérémy Pecourneau
AU - Alejandro García-Eguizábal
AU - Daniil Tkatchev
AU - Raúl Losantos
AU - Christoph Kerzig
AU - Ignacio Funes-Ardoiz
AU - Johannes M. Wahl
PY - 2026
DA - 2026/09/03
PB - ChemRxiv
DO - 10.26434/chemrxiv.15008235/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008235/v1
AB - The photochemistry of carbonyl compounds underpins a wide range of modern synthetic transformations. However, photoinduced rearrangements, despite their unique potential for skeletal reorganization, remain conspicuously underexplored. Here, we show that fluorine can be used as a design principle to divert these reactions from established photochemical pathways. Mechanistic investigations combining experimental, spectroscopic and computational approaches support an unusual singlet excited state pathway involving initial cyclization followed by skeletal rearrangement. This sequence enables the formation of carbonyl ylide 1,3-dipoles, while exhibiting a pronounced increase in polarization along the reaction path. The high efficiency and selectivity of the process provide an attractive platform for isomerization and photoclick chemistry, while its compatibility with water and oxygen broadens the potential for bioorthogonal applications.
ER -