2,6,,9-trioxabicyclo[3.3.1]nona-3,7-dienes and 2,4,6,8-tetraoxaadamantanes: Novel chiral spacer units in macrocyclic polyethers

Wallfisch, Bianca C., Egger, Tamara, Heilmayer, Werner, Kappe, C. Oliver, Wentrup, Curt, Gloe, Karsten, Belaj, Ferdinand, Klintschar, Gerd and Kollenz, Gert (2002) 2,6,,9-trioxabicyclo[3.3.1]nona-3,7-dienes and 2,4,6,8-tetraoxaadamantanes: Novel chiral spacer units in macrocyclic polyethers. Supramolecular Chemistry, 14 5: 383-396. doi:10.1080/1061027021000003430


Author Wallfisch, Bianca C.
Egger, Tamara
Heilmayer, Werner
Kappe, C. Oliver
Wentrup, Curt
Gloe, Karsten
Belaj, Ferdinand
Klintschar, Gerd
Kollenz, Gert
Title 2,6,,9-trioxabicyclo[3.3.1]nona-3,7-dienes and 2,4,6,8-tetraoxaadamantanes: Novel chiral spacer units in macrocyclic polyethers
Journal name Supramolecular Chemistry   Check publisher's open access policy
ISSN 1061-0278
Publication date 2002-01-01
Sub-type Article (original research)
DOI 10.1080/1061027021000003430
Volume 14
Issue 5
Start page 383
End page 396
Total pages 14
Place of publication UK
Publisher Taylor and Francis
Language eng
Subject C1
250303 Physical Organic Chemistry
780103 Chemical sciences
Abstract The unusual chiral heterocyclic systems, trioxabicyclo[3.3.1]nona-3,7-dienes (bridged bisdioxines), are incorporated as novel spacer molecules into macrocyclic polyether ring systems of various sizes (8, 9 as well as 11-15) by cyclocondensation reaction of the! bisacid chloride 4b or bisesters 6,7 and 10, with several ethylene glycols. The 2:2 macrocycles 12-14 are obtained in approximately 50:50 mixtures of diastereomers. These conclusions are mainly based on HPLC data presented in Table I as well as X-ray analyses of (1R,5R)-8c (space group Pbca, a = 10.163(3) Angstrom, b = 18.999(4) Angstrom, c = 36.187(10) Angstrom, V = 6987(3) Angstrom(3), Z = 8, d(calc) = 1.218 g cm(-3), 6974 reflections, R = 0.0553.), mesolrac-11 (space group P (1) over bar, a = 10.472(5) Angstrom, b = 16.390(5) Angstrom, c = 17.211(5) Angstrom, alpha = 98.69(2)degrees, beta = 93.04(2)degrees, gamma = 98.52(2)degrees, V = 2879.3(18) Angstrom(3), Z = 2, d(calc) = 1.173 g cm(-3), 11,162 reflections, R = 0.0945) and meso-12 (space group P2(1)/c, a = 9.927(2), b = 18.166(3), c = 17.820(3) Angstrom, beta = 96.590(10)degrees, V = 3192.3(10)Angstrom(3), Z = 4, D-c = 1.109 g cm(-3), 3490 reflections, R = 0.0646). The 1:1 macrocycles 8b,c are also formed by intramolecular transesterification of the open-chain bisesters 7b,c and their formation is favored by the use of metal ions as templates. The bridged bisdioxine moieties in 8b and 12 are converted into the corresponding chiral tetra-oxaadamantane spacers to afford macrocycles 16 and 17. Preliminary metal ion complexation studies with selected species (8c, 11-14) were also performed.
Keyword Chemistry, Multidisciplinary
Tetraoxaadamantanes
Novel Chiral Spacer Units
Macrocyclic Polyethers
Hplc
Bridged Bisdioxines
X-ray
Bridged Bis-dioxines
Binding-properties
Nmr-spectroscopy
Crown-ethers
Dipivaloylketene
Extraction
Ligands
Design
Q-Index Code C1

Document type: Journal Article
Sub-type: Article (original research)
Collection: School of Chemistry and Molecular Biosciences
 
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Created: Wed, 15 Aug 2007, 03:30:29 EST