The Cascade Reactions of Indigo with Propargyl Substrates for Heterocyclic and Photophysical Diversity |
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| Authors: | Patrick M McCosker Dr Nicholas M Butler Dr Alireza Shakoori Dr Michel K Volland Matthew J Perry Jesse W Mullen Dr Anthony C Willis Prof Timothy Clark Prof John B Bremner Prof Dirk M Guldi Prof Paul A Keller |
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| Institution: | 1. School of Chemistry & Molecular Bioscience, Molecular Horizons, Illawarra Health & Medical Research Institute, University of Wollongong, Northfields Avenue, 2522 Wollongong, NSW, Australia;2. Department of Chemistry and Pharmacy, Interdisciplinary Center for Molecular Materials (ICMM), Chair of Physical Chemistry I, Friedrich-Alexander-Universität Erlangen–Nürnberg (FAU), Egerlandstrasse 3, 91058 Erlangen, Germany;3. Research School of Chemistry, The Australian National University, Canberra, Australian Capital Territory, 2601 Australia;4. Department of Chemistry and Pharmacy, Computer-Chemistry-Center (CCC), Friedrich-Alexander-Universität Erlangen–Nürnberg (FAU), Nägelbachstrasse 25, 91052 Erlangen, Germany |
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| Abstract: | The synthesis of structurally diverse heterocycles for chemical space exploration was achieved via the cascade reactions of indigo with propargylic electrophiles. New pyrazinodiindolodione, naphthyridinedione, azepinodiindolone, oxazinoindolone and pyrrolodione products were prepared in one pot reactions by varying the leaving group (-Cl, -Br, -OMs, -OTs) or propargyl terminal functionality (-H, -Me, -Ph, -Ar). Mechanistic and density functional theory studies revealed that the unsaturated propargyl moiety can behave as an electrophile when aromatic terminal substitutions are made, and therefore competes with leaving group substitution for new outcomes. Selected products from the cascade reactions were investigated for their absorption and fluorescence properties, including transient absorption spectroscopy. This revealed polarity dependent excited state relaxation pathways, fluorescence, and triplet formation, thus highlighting these reactions as a means to access diverse functional materials rapidly. |
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| Keywords: | density functional calculations domino reactions dyes/pigments molecular diversity photophysics |
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