Resolution of a Configurationally Stable Hetero[4]helicene.

Michela Lupi,Caterina Viglianisi,Martina Onori,Stefano Menichetti,Sergio Abbate,Giovanna Longhi

doi:10.3390/molecules27041160

Michela Lupi, Caterina Viglianisi + Show 4 more

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https://doi.org/10.3390/molecules27041160

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Abstract

We have developed an efficient chemical resolution of racemic hydroxy substituted dithia-aza[4]helicenes (DTA[4]H) 1(OH) using enantiopure acids as resolving agents. The better diastereomeric separation was achieved on esters prepared with (1S)-(−)-camphanic acid. Subsequent simple manipulations produced highly optically pure (≥ 99% enantiomeric excess) (P) and (M)-1(OH) in good yields. The role of the position where the chiral auxiliary is inserted (cape- vs. bay-zone) and the structure of the enantiopure acid used on successful resolution are discussed.

Highlights

Chirality is one of the most crucial assets of nature and is of paramount importance in several areas of science, technology and medicine
We decided to study the insertion of chiral auxiliaries, for example through esterification reactions, to verify whether the mixture of diastereomers obtained can be separated by flash chromatography allowing isolation of pure M and P DTA[4]H in relevant quantity
We decided to study the insertion of chiral auxiliaries, for example4 of 16 through esterification reactions, to verify whether the mixture of diastereomers obtained can be separated by flash chromatography allowing isolation of pure M and P DTA[4]H

Summary

Introduction

Chirality is one of the most crucial assets of nature and is of paramount importance in several areas of science, technology and medicine. Helicenes are compounds with a screw-shaped skeleton formed by ortho-condensed (hetero)aromatic rings with a non-planar structure due to the steric superimposition of terminal rings or/and the substituents on these rings [2], which force the molecule to adopt a helical conformation (Figure 1). This important class of axially chiral compounds has a barrier of interconversion between M and P enantiomers increasing with the increase of the ring number forming the helicene backbone

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