Investigation of macrocyclisation routes to 1,4,7-triazacyclononanes : efficient syntheses from 1,2-ditosylamides
Stones, G. and Tripoli, Régis and McDavid, Colin L. and Roux-Duplatre, Kewin and Kennedy, A.R. and Sherrington, D.C. and Gibson, C.L. (2008) Investigation of macrocyclisation routes to 1,4,7-triazacyclononanes : efficient syntheses from 1,2-ditosylamides. Organic and Biomolecular Chemistry, 6 (2). pp. 374-384. ISSN 1477-0520
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Abstract
Two routes to the synthesis of a cyclohexyl-fused 1,4,7-triazacyclononane involving macrocyclisations of tosamides have been investigated. In the first approach, using a classic Richman-Atkins-type cyclisation of a cyclohexyl-substituted 1,4,7-tritosamide with ethylene glycol ditosylate, afforded the cyclohexyl-fused 1,4,7-triazacyclononane in 5.86% overall yield in four steps. The second, more concise, approach involving the macrocyclisation of trans-cyclohexane-1,2-ditosamide with the tritosyl derivative of diethanolamine initially gave poor yields (< 25%). The well-documented problems with efficiencies in macrocyclisations using 1,2-ditosamides led to the use of a wider range of 1,2-ditosamides including ethane-1,2-ditosamide and propane-1,2-ditosamide. These extended studies led to the development of an efficient macrocyclisation protocol using lithium hydride. This new method afforded 1,4,7-tritosyl-1,4,7-triazacyclononanes in good yield (57-90%) from 1,2-ditosamides in a single step. These efficient methods were then applied to the preparation of a chiral cyclohexyl-fused 1,4,7-tritosyl-1,4,7-triazacyclononane (65-70%). This key chiral intermediate was then converted into a copper(II) complex following detosylation and N-methylation. The resulting chiral copper(II) complex catalysed the aziridination of styrene but it did so in a racemic fashion.
Creators(s): |
Stones, G., Tripoli, Régis, McDavid, Colin L., Roux-Duplatre, Kewin, Kennedy, A.R. ![]() ![]() | Item type: | Article |
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ID code: | 19843 |
Keywords: | chiral aziridines, crystal structure, dynamic behavior, model complexes, ring closure, ligands, Chemistry, Biochemistry, Organic Chemistry, Physical and Theoretical Chemistry |
Subjects: | Science > Chemistry |
Department: | Faculty of Science > Pure and Applied Chemistry |
Depositing user: | Strathprints Administrator |
Date deposited: | 04 Jun 2010 13:49 |
Last modified: | 01 Jan 2021 04:36 |
URI: | https://strathprints.strath.ac.uk/id/eprint/19843 |
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