Synthesis of 5,9‐Diaza Analogues of [5]‐ and [6]Helicene and their Chiroptic and Photophysical Characterization

Author:

Herzog Stefan1ORCID,Rizzo Gianluca Giuseppe1ORCID,Podlech Joachim1ORCID

Affiliation:

1. Institut für Organische Chemie Karlsruher Institut für Technologie (KIT) 76131 Karlsruhe Kaiserstraße 12 Germany

Abstract

Abstract6,10‐Dipropyl‐5,9‐diaza[5]‐ and ‐[6]helicene were synthesized by ortho,ortho’ fusion of ortho‐teraryldicarboxamides. Key steps in the synthesis of the teraryls are azide formation with subsequent reduction and amidation followed by Suzuki cross couplings. The ortho fusions were achieved with phosphorus pentoxide and phosphoryl oxide. The total syntheses could be accomplished with 10 % and 3 %, respectively, in seven consecutive steps starting with meta‐dibromobenzene. The helicenes were investigated by UV/Vis and fluorescence spectroscopy and by quantum chemical calculation of, inter alia, the HOMO‐LUMO gaps. Racemization barriers of the helicenes were calculated, whereupon the optical resolution of 5,9‐diaza[6]helicene was attempted and carried out successfully; ECD spectra were measured of its enantiomers.

Funder

Deutsche Forschungsgemeinschaft

Publisher

Wiley

Reference125 articles.

1.  

2. Die Helicene

3. The Helicenes

4. Helicenes: Synthesis and Applications

5. C.-F. Chen Y. Shen Helicene Chemistry – From Synthesis to Applications Springer-Verlag Berlin Heidelberg 2017;

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