Oxidative Cyclodehydrogenation Reactions with Tetraarylporphyrins. Issue 43 (11th November 2020)

• Record Type: Journal Article
• Authors: Martin, Max M.; Oleszak, Christoph; Hampel, Frank; Jux, Norbert
• Is Part Of: European journal of organic chemistry. Issue 43(2020)
• Page Start: 6758
• Page End: 6762
• Publication Date: 2020-11-11
• Subjects: π‐Extension -- Porphyrinoids -- Fusion reaction -- Scholl oxidation -- Post‐functionalization; Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1002/ejoc.202001174
• Languages: English
• ISSNs: 1434-193X

Abstract

Abstract : The extension of the aromatic π‐system of porphyrins is a powerful method to alter their optoelectronic properties. Herein, aryl substituents were fused to porphyrin cores by Scholl oxidation reactions that selectively produced mono‐ and doubly‐fused porphyrins in yields of up to 69 %. Several different aryl substituents attached to the porphyrin were investigated with respect to their reactivity under Scholl conditions. The fused products were fully characterized, i.e., by UV/Vis absorption spectroscopy, which showed drastic changes in the electronic features. Insight into the solid‐state behavior was obtained by X‐ray crystallography. Our approach represents a novel option for the late‐stage functionalization of porphyrin‐based compounds. Abstract : The transformation of A 4 ‐symmetric nickel porphyrins to the respective π‐extended derivatives via a Scholl oxidative route is presented. Different meso ‐aryl substituents were successfully fused to the porphyrin core using standard Scholl conditions. The photophysical characteristics of fused‐porphyrins were significantly different to the non‐fused derivatives. Insight into the solid‐state properties was obtained by X‐ray crystallography.