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Crystallographic proof of double Walden inversion in nucleophilic substitution reactions of macrocyclic cyclotriphosphazene derivatives

Crystallographic proof of double Walden inversion in nucleophilic substitution reactions of macrocyclic cyclotriphosphazene derivatives
Crystallographic proof of double Walden inversion in nucleophilic substitution reactions of macrocyclic cyclotriphosphazene derivatives
Using X-ray crystallography it is demonstrated unambiguously that a double Walden inversion reaction occurs for suc-cessive nucleophilic substitution of the mono-spiropropanoxy-amino derivative of the cis-ansa-macrocyclic cyclophosphazene compound N3P3[O(CH2)3NH][O(CH2CH2O)4]Cl2 (3). The spiropropanoxyamino moiety enables groups above and below the plane of the N3P3 ring to be distinguished. The first nucleophilic substitution of compound 3 with X- (e.g., X = 2-naphthoxy) gives N3P3[O(CH2)3NH][O(CH2CH2O)4]XCl (4a), which has a trans-ansa-macrocyclic ring as a result of the inversion reaction, and then subsequent reaction of 4a with the same nucleophile gives N3P3[O(CH2)3NH][O(CH2CH2O)4]X2 (5a), in which the macrocyclic ring is cis-ansa again, but it is now on the opposite side of the N3P3 ring from that of the starting material 3 as a result of the second inversion reaction. Structures stereochemically analogous to compound 5a were also obtained upon reaction with other monofunctional nucleophiles, such as phenol, pyrrolidine and aniline, to give compounds 5b, 5c and 5d, respectively, and with the difunctional nucleophile 2,2,3,3-tetrafluorobutanediol to give the di-ansa derivative 6. Compound 3 was also sequentially treated with two different mononucleophiles - phenol and aniline - to give the unsymmetrically disubstituted compound 7, in which the macrocyclic ring is also cis-ansa again and on the opposite side of the N3P3 ring from that of the starting material, as a result of the double Walden inversion reactions.
nucleophilic substitution, inversion of configuration, cyclotriphosphazenes, crystal structures, configuration determination, cyclophosphazenes, aminolysis
1434-1948
959-966
Beşli, Serap
63ec1cf4-d0d6-4982-9e0a-c632f1f98d08
Coles, Simon J.
65bb28e4-4917-43f5-a770-a00017d6783f
Davies, David B.
675b90e6-0c3c-468b-9996-326220517cc6
Eaton, Robert J.
e274676b-0499-47e1-8dbb-8d1ed908cdea
Hursthouse, Michael B.
a65b4d35-2ea0-47e7-938a-d744f4d9ba28
Kiliç, Adem
53892b58-c3f9-4894-bdf9-6be70ab7611e
Shaw, Robert A.
a9ecde60-6fe9-4b5d-86e3-77cd5dcfaab8
Beşli, Serap
63ec1cf4-d0d6-4982-9e0a-c632f1f98d08
Coles, Simon J.
65bb28e4-4917-43f5-a770-a00017d6783f
Davies, David B.
675b90e6-0c3c-468b-9996-326220517cc6
Eaton, Robert J.
e274676b-0499-47e1-8dbb-8d1ed908cdea
Hursthouse, Michael B.
a65b4d35-2ea0-47e7-938a-d744f4d9ba28
Kiliç, Adem
53892b58-c3f9-4894-bdf9-6be70ab7611e
Shaw, Robert A.
a9ecde60-6fe9-4b5d-86e3-77cd5dcfaab8

Beşli, Serap, Coles, Simon J., Davies, David B., Eaton, Robert J., Hursthouse, Michael B., Kiliç, Adem and Shaw, Robert A. (2005) Crystallographic proof of double Walden inversion in nucleophilic substitution reactions of macrocyclic cyclotriphosphazene derivatives. European Journal of Inorganic Chemistry, (5), 959-966. (doi:10.1002/ejic.200400745).

Record type: Article

Abstract

Using X-ray crystallography it is demonstrated unambiguously that a double Walden inversion reaction occurs for suc-cessive nucleophilic substitution of the mono-spiropropanoxy-amino derivative of the cis-ansa-macrocyclic cyclophosphazene compound N3P3[O(CH2)3NH][O(CH2CH2O)4]Cl2 (3). The spiropropanoxyamino moiety enables groups above and below the plane of the N3P3 ring to be distinguished. The first nucleophilic substitution of compound 3 with X- (e.g., X = 2-naphthoxy) gives N3P3[O(CH2)3NH][O(CH2CH2O)4]XCl (4a), which has a trans-ansa-macrocyclic ring as a result of the inversion reaction, and then subsequent reaction of 4a with the same nucleophile gives N3P3[O(CH2)3NH][O(CH2CH2O)4]X2 (5a), in which the macrocyclic ring is cis-ansa again, but it is now on the opposite side of the N3P3 ring from that of the starting material 3 as a result of the second inversion reaction. Structures stereochemically analogous to compound 5a were also obtained upon reaction with other monofunctional nucleophiles, such as phenol, pyrrolidine and aniline, to give compounds 5b, 5c and 5d, respectively, and with the difunctional nucleophile 2,2,3,3-tetrafluorobutanediol to give the di-ansa derivative 6. Compound 3 was also sequentially treated with two different mononucleophiles - phenol and aniline - to give the unsymmetrically disubstituted compound 7, in which the macrocyclic ring is also cis-ansa again and on the opposite side of the N3P3 ring from that of the starting material, as a result of the double Walden inversion reactions.

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Published date: 4 March 2005
Keywords: nucleophilic substitution, inversion of configuration, cyclotriphosphazenes, crystal structures, configuration determination, cyclophosphazenes, aminolysis

Identifiers

Local EPrints ID: 20725
URI: https://eprints.soton.ac.uk/id/eprint/20725
ISSN: 1434-1948
PURE UUID: c3c157a4-537b-4c46-8fd1-584adaaf3406

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Date deposited: 01 Mar 2006
Last modified: 17 Jul 2017 16:28

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Contributors

Author: Serap Beşli
Author: Simon J. Coles
Author: David B. Davies
Author: Robert J. Eaton
Author: Michael B. Hursthouse
Author: Adem Kiliç
Author: Robert A. Shaw

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