Synthesis of Racemic, Diastereopure, and Enantiopure Carba- or Oxa[5]‑, [6]‑, [7]‑, and -[19]helicene (Di)thiol Derivatives

A series of carba- or oxa[5]-, [6]-, [7]-, and -[19]­helicene (di)­thiols was prepared. The Miyazaki–Newman–Kwart rearrangement of (dimethylcarbamothioyl)­oxy (oxa)­helicenes in a flow reactor or nucleophilic substitution of dichloro (oxa)­helicenes with alkanethiolates were used in the sulfanylatio...

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Published in:Journal of organic chemistry 2020-01, Vol.85 (1), p.248-276
Main Authors: Nejedlý, Jindřich, Šámal, Michal, Rybáček, Jiří, Sánchez, Isabel Gay, Houska, Václav, Warzecha, Tomáš, Vacek, Jaroslav, Sieger, Ladislav, Buděšínský, Miloš, Bednárová, Lucie, Fiedler, Pavel, Císařová, Ivana, Starý, Ivo, Stará, Irena G
Format: Article
Language:English
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Summary:A series of carba- or oxa[5]-, [6]-, [7]-, and -[19]­helicene (di)­thiols was prepared. The Miyazaki–Newman–Kwart rearrangement of (dimethylcarbamothioyl)­oxy (oxa)­helicenes in a flow reactor or nucleophilic substitution of dichloro (oxa)­helicenes with alkanethiolates were used in the sulfanylation step. Despite the high temperatures employed in this key step, no conformational scrambling was observed during the asymmetric synthesis of the diastereo- and enantiopure oxahelicenes. Single-molecule conductivity of the longest oxa[19]­helicene dithiol derivative was studied by the scanning tunneling microscopy break-junction method.
ISSN:0022-3263
1520-6904
DOI:10.1021/acs.joc.9b02965