Synthesis, Chiral Resolution, and Optical Properties of 2,18-Dihydoxy-5,10,15-trioxa[9]helicene

0539547 - ÚOCHB 2022 RIV DE eng J - Journal Article
Shyam Sundar, Mothuku - Klepetářová, Blanka - Bednárová, Lucie - Muller, G.
Synthesis, Chiral Resolution, and Optical Properties of 2,18-Dihydoxy-5,10,15-trioxa[9]helicene.
European Journal of Organic Chemistry. Roč. 2021, č. 1 (2021), s. 146-150. ISSN 1434-193X. E-ISSN 1099-0690
Institutional support: RVO:61388963
Keywords : chiral HPLC * circular dichroism * helicenes * heterohelicenes * enantiomers * optical properties
OECD category: Organic chemistry
Impact factor: 3.261, year: 2021
Method of publishing: Limited access
https://doi.org/10.1002/ejoc.202001177

Herein, we report a simple and efficient approach to synthesize a functionalized 2,18-dimethoxy-5,10,15-trioxa[9]helicene. It was synthesized from simple phenol building blocks using two subsequent reactions namely oxidative coupling and dehydrative cyclization or palladium mediated cyclization. The molecular integrity of the helical core was determined by single-crystal X-ray diffraction and NMR techniques. Its crystal structure showed the spontaneous resolution which was attributed to the conglomerate formation of the same helical isomer via C−H⋅⋅⋅O and π⋅⋅⋅π or H⋅⋅⋅π interactions. Then, it was converted to racemic 2,18-dihydoxy-5,10,15-trioxa[9]helicene. Enantiomers were separated on preparative HPLC with high optical purity (>99 % ee). Based on electronic circular dichroism, the absolute configurations of dextrorotary and levorotatory antipodes were assigned as P and M, respectively. We also studied the absorption, emission and chiroptical behavior of these helical compounds in the solution state.
Permanent Link: http://hdl.handle.net/11104/0318114