Donor-Acceptor 1,2,4,5-Tetrazines Prepared by the Buchwald-Hartwig Cross-Coupling Reaction and Their Photoluminescence Turn-On Property by Inverse Electron Demand Diels-Alder Reaction

Yangyang Qu; Piotr Pander; Oleh Vybornyi; Marharyta Vasylieva; Régis Guillot; Fabien Miomandre; Fernando B Dias; Peter Skabara; Przemyslaw Data; Gilles Clavier; Pierre Audebert

doi:10.1021/acs.joc.9b02817

Donor-Acceptor 1,2,4,5-Tetrazines Prepared by the Buchwald-Hartwig Cross-Coupling Reaction and Their Photoluminescence Turn-On Property by Inverse Electron Demand Diels-Alder Reaction

J Org Chem. 2020 Mar 6;85(5):3407-3416. doi: 10.1021/acs.joc.9b02817. Epub 2020 Feb 12.

Authors

Affiliations

¹ PPSM, CNRS, ENS Paris-Saclay, 61 Avenue Président Wilson, 94235 Cachan, France.
² Physics Department, Durham University, South Road, Durham DH1 3LE, U.K.
³ WestCHEM, School of Chemistry, University of Glasgow, Glasgow G12 8QQ, U.K.
⁴ Silesian University of Technology, Faculty of Chemistry, Department of Physical Chemistry and Technology of Polymers, M. Stzody 9, 44-100 Gliwice, Poland.
⁵ Centre of Polymer and Carbon Materials of the Polish Academy of Sciences, 41-819 Zabrze, Poland.
⁶ Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Université Paris-Sud 11, Université Paris-Saclay, UMR CNRS 8182, Rue du doyen Georges Poitou, 91405 Orsay Cedex, France.

PMID: 31975598
DOI: 10.1021/acs.joc.9b02817

Abstract

A facile efficient synthetic tool, Buchwald-Hartwig cross-coupling reaction, for the functionalization of 1,2,4,5-tetrazines is presented. Important factors affecting the Buchwald-Hartwig cross-coupling reaction have been optimized. Seven new donor-acceptor tetrazine molecules (TA1-TA7) were conveniently prepared in good to high yields (61-72%). They have been subsequently engaged in the inverse electron demand Diels-Alder (iEDDA) reaction with cyclooctyne. The photophysical and electrochemical properties of the new pyridazines have been studied. Some are fluorescent acting as turn-on probes. More importantly, two pyridazines (DA3 and DA6) exhibit room-temperature phosphorescence (RTP) properties.