Premium
The Cascade Reactions of Indigo with Propargyl Substrates for Heterocyclic and Photophysical Diversity
Author(s) -
McCosker Patrick M.,
Butler Nicholas M.,
Shakoori Alireza,
Volland Michel K.,
Perry Matthew J.,
Mullen Jesse W.,
Willis Anthony C.,
Clark Timothy,
Bremner John B.,
Guldi Dirk M.,
Keller Paul A.
Publication year - 2021
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202003662
Subject(s) - propargyl , moiety , electrophile , chemistry , photochemistry , fluorescence , indigo , combinatorial chemistry , functional group , organic chemistry , catalysis , art , physics , polymer , quantum mechanics , visual arts
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.