The preparation and absolute configurations of enantiomerically pure C4-symmetric tetraalkoxyresorcin[4]arenes obtained from camphorsulfonate derivatives

Buckley, Benjamin R., Bulman Page, Philip C., Chan, Yohan, Heaney, Harry, Klaes, Michael, McIldowie, Matthew J., McKee, Vickie, Mattay, Jochen, Mocerino, Mauro, Moreno, Eduardo, Skelton, Brian W. and White, Allan H. (2006) The preparation and absolute configurations of enantiomerically pure C4-symmetric tetraalkoxyresorcin[4]arenes obtained from camphorsulfonate derivatives. European Journal of Organic Chemistry, 2006 (22). pp. 5135-5151. ISSN 1434-193X

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Abstract

The preparation of a series of diastereoisomeric tetracamphorsulfonates derived from racemic tetramethoxyresorcin[4]arenes was achieved by reactions with an excess of (S)(+)-10-camphorsulfonyl chloride in pyridine followed by isolation using flash chromatography. Tetradeprotonation of a number of tetramethoxyresorcin[4]arenes using n-butyllithium in tetrahydrofuran, followed by reactions using (S)-(+)10-camphorsulfonyl chloride, gave the same tetracamphorsulfonates. Mono-, di- and tricamphorsulfonates were also prepared following selective deprotonation. In the reactions with tetraisopropyloxy- and tetracyclopentyloxyresorcin[4]arenes, only the mono- and dicamphorsulfonates were formed. X-ray crystallographic analysis established the absolute configurations of three diastereoisomerically pure tetracamphorsulfonates, including a diastereoisomer prepared from 6,12,18,24-tetramethoxy-2,8,14,20-tetrakis(2-methylpropyl)resorcin[4]are ne. An additional pair of diastereoisomers was also prepared using (R)-(-)-10-camphorsulfonyl chloride and 6,12,18,24-tetramethoxy-2,8,14,20-tetrakis(2-methylpropyl)resorcin[4]are ne, for one of which the structure was confirmed by an additional X-ray structure determination. Hydrolytic removal of the camphorsulfonyl residue(s) from the various diastereoisomers gave enantiomers of known absolute configurations. In some cases, the chiral nonracemic tetraalkoxyresorcin[4]arenes were converted into known tetrabenzoxazine derivatives by using N,N-bis(methoxymethyl)[(S)-(-)-(a-methylbenzyl)]amine in thermal or microwave - assisted reactions. (c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006.

Item Type: Article
Uncontrolled Keywords: mitteilung,acid,resorcinarenes,cyclodiastereomerie,diastereoselectivity,chirality,calixarenes,camphorsulfonates,determination,hydrolysis,chiral auxiliaries,binaphthyl crown unit,optical resolution,calix<4>arenes,axial chirality,cycloenantiomerie,mannich reactions,configuration,resorcin[4]arenes
Faculty \ School: Faculty of Science > School of Chemistry
Depositing User: Rachel Smith
Date Deposited: 20 Jun 2011 15:34
Last Modified: 21 Apr 2020 19:40
URI: https://ueaeprints.uea.ac.uk/id/eprint/32871
DOI: 10.1002/ejoc.200600591

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