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The Cascade Reactions of Indigo with Propargyl Substrates for Heterocyclic and Photophysical Diversity

Journal Article


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.

Publication Date


  • 2021

Citation


  • McCosker, P. M., Butler, N. M., Shakoori, A., Volland, M. K., Perry, M. J., Mullen, J. W., . . . Keller, P. A. (2021). The Cascade Reactions of Indigo with Propargyl Substrates for Heterocyclic and Photophysical Diversity. Chemistry - A European Journal, 27(11), 3708-3721. doi:10.1002/chem.202003662

Scopus Eid


  • 2-s2.0-85101475731

Start Page


  • 3708

End Page


  • 3721

Volume


  • 27

Issue


  • 11

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.

Publication Date


  • 2021

Citation


  • McCosker, P. M., Butler, N. M., Shakoori, A., Volland, M. K., Perry, M. J., Mullen, J. W., . . . Keller, P. A. (2021). The Cascade Reactions of Indigo with Propargyl Substrates for Heterocyclic and Photophysical Diversity. Chemistry - A European Journal, 27(11), 3708-3721. doi:10.1002/chem.202003662

Scopus Eid


  • 2-s2.0-85101475731

Start Page


  • 3708

End Page


  • 3721

Volume


  • 27

Issue


  • 11