Isoguanine (2-Hydroxyadenine) and 2-Aminoadenine Nucleosides with an 8-Aza-7-deazapurine Skeleton: Synthesis, Functionalization with Fluorescent and Clickable Side Chains, and Impact of 7-Substituents on Physical Properties

DC FieldValueLanguage
dc.contributor.authorKondhare, Dasharath
dc.contributor.authorLeonard, Peter
dc.contributor.authorSeela, Frank
dc.date.accessioned2021-12-23T16:06:17Z-
dc.date.available2021-12-23T16:06:17Z-
dc.date.issued2021
dc.identifier.issn00223263
dc.identifier.urihttps://osnascholar.ub.uni-osnabrueck.de/handle/unios/7342-
dc.description.abstract7-Functionalized 8-aza-7-deaza-2'-deoxyisoguanine and 8-aza-7-deaza-2-aminoadenine 2'-deoxyribonucleosides decorated with fluorescent pyrene or benzofuran sensor tags or clickable side chains with terminal triple bonds were synthesized. 8-Aza-7-deaza-7-iodo-2-amino-2'-deoxyadenosine was used as the central intermediate and was accessible by an improved two-step glycosylation/amination protocol. Functionalization of position-7 was performed either on 8-aza-7-deaza-7-iodo-2-amino-2'-deoxyadenosine followed by selective deamination of the 2-amino group or on 7-iodinated 8-aza-7-deaza-2'-deoxyisoguanosine. Sonogashira and Suzuki-Miyaura cross-coupling reactions were employed for this purpose. Octadiynyl side chains were selected as linkers for click reactions with azido pyrenes. K-Taut values calculated from H2O/dioxane mixtures revealed that side chains have a significant influence on the tautomeric equilibrium. Photophysical properties (fluorescence, solvatochromism, and quantum yields) of the new 8-aza-7-deazapurine nucleosides with fluorescent side chains were determined. Remarkably, a strong excimer fluorescence in H2O was observed for pyrene dye conjugates of 8-aza-7-deazaisoguanine and 2-aminoadenine nucleosides with a long linker. In other solvents including methanol, excimer fluorescence was negligible. The 2-aminoadenine and isoguanine nucleosides with the 8-aza-7-deazapurine skeleton expand the class of nucleosides applicable to fluorescence detection with respect to diagnostic and therapeutic purposes.
dc.description.sponsorshipChemBiotech, Munster, Germany; We acknowledge Dr. Simone Budow-Busse for critical reading of the manuscript. We would like to thank Dr. Letzel, Organisch-Chemisches Institut, Universitat Munster, Germany, for the measurement of the ESI-TOF mass spectra and Prof. Dr. B. Wunsch, Institut fur Pharmazeutische und Medizinische Chemie, Universitat Munster, for providing us with 600 MHz NMR spectra and mass spectra. We appreciate the technical assistance of Chaitali Kaldate. Funding by ChemBiotech, Munster, Germany, is gratefully acknowledged.
dc.language.isoen
dc.publisherAMER CHEMICAL SOC
dc.relation.ispartofJOURNAL OF ORGANIC CHEMISTRY
dc.subject2'-DEOXYISOGUANOSINE
dc.subject2-DEOXYISOGUANOSINE
dc.subjectANALOGS
dc.subjectBASE-PAIRING PROPERTIES
dc.subjectChemistry
dc.subjectChemistry, Organic
dc.subjectDNA
dc.subjectISOGUANOSINE
dc.subjectOLIGONUCLEOTIDE DUPLEXES
dc.subjectPARALLEL
dc.subjectSOLVENT
dc.subjectTAUTOMERISM
dc.titleIsoguanine (2-Hydroxyadenine) and 2-Aminoadenine Nucleosides with an 8-Aza-7-deazapurine Skeleton: Synthesis, Functionalization with Fluorescent and Clickable Side Chains, and Impact of 7-Substituents on Physical Properties
dc.typejournal article
dc.identifier.doi10.1021/acs.joc.1c01283
dc.identifier.isiISI:000716778300017
dc.description.volume86
dc.description.issue21
dc.description.startpage14461
dc.description.endpage14475
dc.identifier.eissn15206904
dc.publisher.place1155 16TH ST, NW, WASHINGTON, DC 20036 USA
dcterms.isPartOf.abbreviationJ. Org. Chem.
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