Issue 19, 2021

Regio- and stereoselectivity of spirodienone formation in 2,14-dithiacalix[4]arene

Abstract

The oxidation of 2,14-dithiacalix[4]arene with formation of the corresponding mono- and di-spirodienone derivatives was studied to find out which part of the molecule determines the chemical behaviour of this mixed-bridge macrocycle. Interestingly, applying procedures well established in thia- and/or classical calixarene chemistry, for the macrocycle with alternating thiacalixarene and calixarene structural fragments, resulted in the selective formation of the S-spiro derivative. Similar selectivity was also observed for dispiro compounds, indicating that the thiacalixarene fragment (Ar–S–Ar) is much more prone to spirocyclization than the calixarene one (Ar–CH2–Ar). The acid-induced rearrangement of the S-spiro compound led to the corresponding phenoxathiin-based calixarene, representing a novel macrocyclic system. The conformational preferences of the new inherently chiral macrocycles were studied with NMR spectroscopy and single-crystal X-ray analysis complemented by DFT calculations.

Graphical abstract: Regio- and stereoselectivity of spirodienone formation in 2,14-dithiacalix[4]arene

Supplementary files

Article information

Article type
Paper
Submitted
15 Mar 2021
Accepted
05 Apr 2021
First published
06 Apr 2021

New J. Chem., 2021,45, 8563-8571

Regio- and stereoselectivity of spirodienone formation in 2,14-dithiacalix[4]arene

D. Kortus, V. Eigner and P. Lhoták, New J. Chem., 2021, 45, 8563 DOI: 10.1039/D1NJ01257F

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