Issue 8, 2021

Asymmetric systematic synthesis, structures, and (chir)optical properties of a series of dihetero[8]helicenes

Abstract

A series of dihetero[8]helicenes have been systematically synthesized in enantiomerically enriched forms by utilizing the characteristic transformations of the organosulfur functionality. The synthetic route begins with assembling a ternaphthyl common synthetic intermediate from 2-naphthol and bissulfinylnaphthalene through an extended Pummerer reaction followed by facile multi-gram-scale resolution. The subsequent cyclization reactions into dioxa- and dithia[8]helicenes take place with excellent axial-to-helical chirality conversion. Dithia[8]helicene is further transformed into the nitrogen and the carbon analogs by replacing the two endocyclic sulfur atoms via SNAr-based skeletal reconstruction. The efficient systematic synthesis has enabled comprehensive evaluation of physical properties, which has clarified the effect of the endocyclic atoms on their structures and (chir)optical properties as well as the unexpected conformational stability of the common helical framework.

Graphical abstract: Asymmetric systematic synthesis, structures, and (chir)optical properties of a series of dihetero[8]helicenes

Supplementary files

Article information

Article type
Edge Article
Submitted
05 jan 2021
Accepted
28 jan 2021
First published
29 jan 2021
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2021,12, 2784-2793

Asymmetric systematic synthesis, structures, and (chir)optical properties of a series of dihetero[8]helicenes

T. Yanagi, T. Tanaka and H. Yorimitsu, Chem. Sci., 2021, 12, 2784 DOI: 10.1039/D1SC00044F

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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