Unprecedented visible light-initiated topochemical [2 + 2] cycloaddition in a functionalized bimane dye

Bimanes, a class of molecules based on the 1H,7H-pyrazolo[1,2-a]pyrazole-1,7-dione scaffold, were first introduced by E. M. Kosower in 1978. In this study, we report the topochemical cycloaddition of diethyl 2,6-dichloro-1,7-dioxo-1H,7H-pyrazolo[1,2-a]pyrazole-3,5-dicarboxylate (Cl2B), initiated by...

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Main Authors: Metodej Dvoracek, Brendan Twamley, Mathias O. Senge, Mikhail A. Filatov
Format: Article
Language:English
Published: Beilstein-Institut 2025-03-01
Series:Beilstein Journal of Organic Chemistry
Subjects:
Online Access:https://doi.org/10.3762/bjoc.21.37
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author Metodej Dvoracek
Brendan Twamley
Mathias O. Senge
Mikhail A. Filatov
author_facet Metodej Dvoracek
Brendan Twamley
Mathias O. Senge
Mikhail A. Filatov
author_sort Metodej Dvoracek
collection DOAJ
description Bimanes, a class of molecules based on the 1H,7H-pyrazolo[1,2-a]pyrazole-1,7-dione scaffold, were first introduced by E. M. Kosower in 1978. In this study, we report the topochemical cycloaddition of diethyl 2,6-dichloro-1,7-dioxo-1H,7H-pyrazolo[1,2-a]pyrazole-3,5-dicarboxylate (Cl2B), initiated by visible light. Crystal structure analysis confirmed that the reactive double bonds are parallel and coplanar, in line with the Schmidt criteria for topochemical cycloaddition. Additionally, two other bimane derivatives with different substitution patterns were synthesized and investigated. Our findings suggest that functionalizing bimanes to redshift their absorption maxima into the visible-light spectrum provides a promising strategy for synthesizing substituted cyclobutanes without the need for ultraviolet irradiation.
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series Beilstein Journal of Organic Chemistry
spelling doaj-art-ae67dbda34874427a6721ede5d23dd522025-08-20T02:08:15ZengBeilstein-InstitutBeilstein Journal of Organic Chemistry1860-53972025-03-0121150050910.3762/bjoc.21.371860-5397-21-37Unprecedented visible light-initiated topochemical [2 + 2] cycloaddition in a functionalized bimane dyeMetodej Dvoracek0Brendan Twamley1Mathias O. Senge2Mikhail A. Filatov3School of Chemical and Biopharmaceutical Sciences, Technological University Dublin, City Campus, Grangegorman, D07 ADY7 Dublin, Ireland School of Chemistry, Trinity College Dublin, The University of Dublin, Dublin 2, Ireland, School of Chemistry, Trinity College Dublin, The University of Dublin, Trinity Biomedical Sciences Institute, 152-160 Pearse Street, Dublin D02 R590, Ireland School of Chemical and Biopharmaceutical Sciences, Technological University Dublin, City Campus, Grangegorman, D07 ADY7 Dublin, Ireland Bimanes, a class of molecules based on the 1H,7H-pyrazolo[1,2-a]pyrazole-1,7-dione scaffold, were first introduced by E. M. Kosower in 1978. In this study, we report the topochemical cycloaddition of diethyl 2,6-dichloro-1,7-dioxo-1H,7H-pyrazolo[1,2-a]pyrazole-3,5-dicarboxylate (Cl2B), initiated by visible light. Crystal structure analysis confirmed that the reactive double bonds are parallel and coplanar, in line with the Schmidt criteria for topochemical cycloaddition. Additionally, two other bimane derivatives with different substitution patterns were synthesized and investigated. Our findings suggest that functionalizing bimanes to redshift their absorption maxima into the visible-light spectrum provides a promising strategy for synthesizing substituted cyclobutanes without the need for ultraviolet irradiation.https://doi.org/10.3762/bjoc.21.37bimane[2 + 2] cycloadditionfluorescencetopochemical polymerizationx-ray crystallography
spellingShingle Metodej Dvoracek
Brendan Twamley
Mathias O. Senge
Mikhail A. Filatov
Unprecedented visible light-initiated topochemical [2 + 2] cycloaddition in a functionalized bimane dye
Beilstein Journal of Organic Chemistry
bimane
[2 + 2] cycloaddition
fluorescence
topochemical polymerization
x-ray crystallography
title Unprecedented visible light-initiated topochemical [2 + 2] cycloaddition in a functionalized bimane dye
title_full Unprecedented visible light-initiated topochemical [2 + 2] cycloaddition in a functionalized bimane dye
title_fullStr Unprecedented visible light-initiated topochemical [2 + 2] cycloaddition in a functionalized bimane dye
title_full_unstemmed Unprecedented visible light-initiated topochemical [2 + 2] cycloaddition in a functionalized bimane dye
title_short Unprecedented visible light-initiated topochemical [2 + 2] cycloaddition in a functionalized bimane dye
title_sort unprecedented visible light initiated topochemical 2 2 cycloaddition in a functionalized bimane dye
topic bimane
[2 + 2] cycloaddition
fluorescence
topochemical polymerization
x-ray crystallography
url https://doi.org/10.3762/bjoc.21.37
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AT brendantwamley unprecedentedvisiblelightinitiatedtopochemical22cycloadditioninafunctionalizedbimanedye
AT mathiasosenge unprecedentedvisiblelightinitiatedtopochemical22cycloadditioninafunctionalizedbimanedye
AT mikhailafilatov unprecedentedvisiblelightinitiatedtopochemical22cycloadditioninafunctionalizedbimanedye