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Chiral configurations of spermine-bridged cyclotriphosphazatrienes

Chiral configurations of spermine-bridged cyclotriphosphazatrienes
Chiral configurations of spermine-bridged cyclotriphosphazatrienes
Spermine-bridged gem-disubstituted cyclotriphosphazatrienes have been synthesised by two routes. In one route a spermine-bridged cyclophosphazene 2 reacted with monofunctional nucleophiles known to favour gem disubstitution in cyclophosphazene rings (e. g. tert-butylamine) to give 3b, or to favour formation of spiro-derivatives with difunctional nucleophiles (e. g. 1,3-propanediol) to give 3c. In the other route a gem-disubstituted cyclophosphazene (i.e. diphenyl, N3P3Ph2Cl4, compound 4) reacted with spermine to give 3a. The >P(N-spiro) group in each cyclophosphazene ring of 3a-c is stereogenic and homotopic, and so it is expected, and confirmed, that the spermine-bridged gem-disubstituted cyclotriphosphazatrienes (3a-c) should be chiral and exist in meso and racemic forms. The proton-decoupled P-31 NMR spectroscopy of 3a-c gave rise to two sets of signals in a 1 : 1 ratio consistent with formation of meso and racemic forms. The meso and racemic forms of 3a (gem-diphenyl derivative) were separated by column chromatography and characterised by X-ray crystallography; this enabled the unequivocal assignment of the two sets of P-31 NMR signals to the meso and racemic forms of 3a. This is the first time that the existence of chiral configurational isomers has been elucidated in the field of spermine-bridged cyclophosphazene compounds, and only the second time in cyclophosphazene chemistry.
phosphorus-nitrogen-compounds, substitution-reactions, cyclophosphazenes, spiro, ansa
1472-7773
365-370
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Davies, David B.
675b90e6-0c3c-468b-9996-326220517cc6
Eaton, Robert J.
e274676b-0499-47e1-8dbb-8d1ed908cdea
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Kiliç, Adem
53892b58-c3f9-4894-bdf9-6be70ab7611e
Mayer, Thomas A.
59bc92dc-0703-4f38-b37d-6e04295371a1
Shaw, Robert A.
a9ecde60-6fe9-4b5d-86e3-77cd5dcfaab8
Yenilmez, Gönül
7754a401-0a85-47c1-9936-1df51ef70654
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Davies, David B.
675b90e6-0c3c-468b-9996-326220517cc6
Eaton, Robert J.
e274676b-0499-47e1-8dbb-8d1ed908cdea
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Kiliç, Adem
53892b58-c3f9-4894-bdf9-6be70ab7611e
Mayer, Thomas A.
59bc92dc-0703-4f38-b37d-6e04295371a1
Shaw, Robert A.
a9ecde60-6fe9-4b5d-86e3-77cd5dcfaab8
Yenilmez, Gönül
7754a401-0a85-47c1-9936-1df51ef70654

Coles, Simon J., Davies, David B., Eaton, Robert J., Hursthouse, Michael B., Kiliç, Adem, Mayer, Thomas A., Shaw, Robert A. and Yenilmez, Gönül (2002) Chiral configurations of spermine-bridged cyclotriphosphazatrienes. Journal of the Chemical Society, Dalton Transactions, (3), 365-370. (doi:10.1039/b104973a).

Record type: Article

Abstract

Spermine-bridged gem-disubstituted cyclotriphosphazatrienes have been synthesised by two routes. In one route a spermine-bridged cyclophosphazene 2 reacted with monofunctional nucleophiles known to favour gem disubstitution in cyclophosphazene rings (e. g. tert-butylamine) to give 3b, or to favour formation of spiro-derivatives with difunctional nucleophiles (e. g. 1,3-propanediol) to give 3c. In the other route a gem-disubstituted cyclophosphazene (i.e. diphenyl, N3P3Ph2Cl4, compound 4) reacted with spermine to give 3a. The >P(N-spiro) group in each cyclophosphazene ring of 3a-c is stereogenic and homotopic, and so it is expected, and confirmed, that the spermine-bridged gem-disubstituted cyclotriphosphazatrienes (3a-c) should be chiral and exist in meso and racemic forms. The proton-decoupled P-31 NMR spectroscopy of 3a-c gave rise to two sets of signals in a 1 : 1 ratio consistent with formation of meso and racemic forms. The meso and racemic forms of 3a (gem-diphenyl derivative) were separated by column chromatography and characterised by X-ray crystallography; this enabled the unequivocal assignment of the two sets of P-31 NMR signals to the meso and racemic forms of 3a. This is the first time that the existence of chiral configurational isomers has been elucidated in the field of spermine-bridged cyclophosphazene compounds, and only the second time in cyclophosphazene chemistry.

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More information

Published date: 2002
Keywords: phosphorus-nitrogen-compounds, substitution-reactions, cyclophosphazenes, spiro, ansa

Identifiers

Local EPrints ID: 19698
URI: http://eprints.soton.ac.uk/id/eprint/19698
ISSN: 1472-7773
PURE UUID: fde50113-c549-46ee-a17c-c368cceed06b
ORCID for Simon J. Coles: ORCID iD orcid.org/0000-0001-8414-9272

Catalogue record

Date deposited: 15 Feb 2006
Last modified: 18 Feb 2021 16:52

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