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Pyrene-Fused [7]Helicenes Connected Via Hexagonal and Heptagonal Rings: Stereospecific Synthesis and Chiroptical Properties

Asim Kumar Swain, Krzysztof Radacki, Holger Braunschweig, Prince Ravat

2022The Journal of Organic Chemistry49 citationsDOI

Abstract

In this manuscript, we portrayed a stereospecific synthesis of C 2 - and C 1 -symmetric pyrene-fused [7]helicene compounds 1 and 2, respectively. Compounds 1 and 2 were synthesized via a one-pot Suzuki coupling–C–H activation and two-step Suzuki coupling–Scholl reaction, respectively, with complete retention of configuration. The synthesized molecules differ in the fusing mode of [7]helicene units with pyrene via six- and seven-membered rings for 1 and 2, respectively. There was a significant difference in the functional properties and enantiomerization barrier of both compounds because of their distinct molecular symmetry as well as fusing mode to pyrene moiety. The heptagon-containing molecule 2 showed remarkable photophysical and chiroptical properties with commendable configurational stability compared to 1 and pristine [7]helicene as well as its [5]helicene congener.

Topics & Concepts

StereospecificityPyreneMoleculeChemistrySymmetry (geometry)CrystallographyStereochemistryHexagonal crystal systemMolecular conformationChirality (physics)Materials scienceCombinatorial chemistrySmall moleculeMolecular modelStereoisomerismComputational chemistryPhotochemistryDensity functional theorySteric effectsSynthesis and Properties of Aromatic CompoundsPhotochromic and Fluorescence ChemistryAxial and Atropisomeric Chirality Synthesis
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