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Chiral Concave Imidazolinium Salts as Precursors to Chiral Concave N-Heterocyclic Carbenes

Winkelmann, Ole
Näther, Christian
Lüning, Ulrich
Published in European Journal of Organic Chemistry. 2007, no. 22, p. 3687-3697
Abstract Imidazolinium moieties have been incorporated into bimacrocycles to generate precursors for concave N-heterocyclic carbenes (NHCs). By using one symmetrically substituted benzene bridgehead and one naphthalene bridgehead devoid of local C2-symmetry, axially chiral concave imidazolinium ions have been obtained. Starting from 2,7-dihydroxy-1-nitronaphthalene (7), the phenol groups have been transformed to 4-pentenyl ethers 8, and the nitro group was then reduced to the corresponding amine 9. Next, 9 and a 2,6-bis(alkenyloxy)aniline 10 were connected by an oxalic acid linker. After reduction of the diamide 13 to diamine 14, a bridge was installed with triethyl orthoformate to give a tetraalkenyl-substituted imidazolinium salt 15. Ring-closing metathesis of 15 followed by hydrogenation of the products 16 yielded the bimacrocyclic salts 17 in 9-18 % overall yield (based on 7), giving amounts up to >300 mg. The configurational stability of 17 was investigated by NMR using chiral enantiopure anions TRISPHAT 18 and BINPHAT 19 as stereodynamic probes.
Keywords Axial chiralityCarbenesChiral anionsMacrocyclesNMR enantiodifferentiationSupramolecular chemistry
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WINKELMANN, Ole et al. Chiral Concave Imidazolinium Salts as Precursors to Chiral Concave N-Heterocyclic Carbenes. In: European Journal of Organic Chemistry, 2007, n° 22, p. 3687-3697. doi: 10.1002/ejoc.200700206 https://archive-ouverte.unige.ch/unige:7746

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Deposited on : 2010-06-21

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