Visible Light-Mediated Homoallylic Radical Rearrangement for the Intermolecular Synthesis of 1,2-Biscyclopropanes
Abstract
1,2-Biscyclopropanes are privileged structural motifs found in natural products, pharmaceuticals, and functional materials, yet their assembly remains challenging. We report the first radical intermolecular strategy for the synthesis of highly functionalized 1,2-biscyclopropanes. Visiblelight-mediated energy transfer (EnT) provides access to a triplet diradical species that, through an ordered intermolecular radical addition, furnishes a rare bis-homoallylic diradical intermediate. This strategy activates the 3-exo-trig radical cyclization triggered by an irreversible intersystem crossing (ISC) step. The method is compatible with naturally occurring functional groups, providing efficient access to polycyclic architectures bearing otherwise inaccessible protic functionalities. Furthermore, the resulting products serve as versatile intermediates for downstream diversification. This work marks a milestone in the development of new mechanistic approaches for the synthesis of highly challenging molecules, highlighting the potential of EnT-enabled diradical reactivity to overcome longstanding limitations in the construction of small rings.
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BibTeX
@misc{serafino2026visible,
title = {{Visible Light-Mediated Homoallylic Radical Rearrangement for the Intermolecular Synthesis of 1,2-Biscyclopropanes}},
author = {Andrea Serafino and Davide Ruggeri and Giulia Russo and Marco Tommaso Barreca and Raimondo Maggi and Francesco Di Maiolo and Daniele Merli and Luciano Marchiò and Nicola Della Ca and Stefano Protti and Giovanni Maestri and Matteo Lanzi},
howpublished = {ChemRxiv},
year = {2026},
month = sep,
doi = {10.26434/chemrxiv.15008450/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008450/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Visible Light-Mediated Homoallylic Radical Rearrangement for the Intermolecular Synthesis of 1,2-Biscyclopropanes
AU - Andrea Serafino
AU - Davide Ruggeri
AU - Giulia Russo
AU - Marco Tommaso Barreca
AU - Raimondo Maggi
AU - Francesco Di Maiolo
AU - Daniele Merli
AU - Luciano Marchiò
AU - Nicola Della Ca
AU - Stefano Protti
AU - Giovanni Maestri
AU - Matteo Lanzi
PY - 2026
DA - 2026/09/07
PB - ChemRxiv
DO - 10.26434/chemrxiv.15008450/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008450/v1
AB - 1,2-Biscyclopropanes are privileged structural motifs found in natural products, pharmaceuticals, and functional materials, yet their assembly remains challenging. We report the first radical intermolecular strategy for the synthesis of highly functionalized 1,2-biscyclopropanes. Visiblelight-mediated energy transfer (EnT) provides access to a triplet diradical species that, through an ordered intermolecular radical addition, furnishes a rare bis-homoallylic diradical intermediate. This strategy activates the 3-exo-trig radical cyclization triggered by an irreversible intersystem crossing (ISC) step. The method is compatible with naturally occurring functional groups, providing efficient access to polycyclic architectures bearing otherwise inaccessible protic functionalities. Furthermore, the resulting products serve as versatile intermediates for downstream diversification. This work marks a milestone in the development of new mechanistic approaches for the synthesis of highly challenging molecules, highlighting the potential of EnT-enabled diradical reactivity to overcome longstanding limitations in the construction of small rings.
ER -