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A cis-directing effect towards diols by an exocyclic P-NHR moiety in cyclotriphosphazenes

A cis-directing effect towards diols by an exocyclic P-NHR moiety in cyclotriphosphazenes
A cis-directing effect towards diols by an exocyclic P-NHR moiety in cyclotriphosphazenes
Cyclophosphazenes containing the P-NHR moiety in an exocyclic spiro ring, N(3)P(3)Cl(4)[NH(CH(2))(3)O], (1), and N(3)P(3)Cl(4)[NH(CH(2))(3)NMe], (2). were used to investigate a possible directing effect of the P-NHR moiety oil the formation of products in the nucleophilic substitution reactions with diols Such as tetraethyleneglycol, 1,3-propanediol and 2,2-dimetliyl-1,3-propanediol. The (31)P NMR spectra of the reaction Mixtures showed that only one kind of ansa product is formed in each of these reactions. X-ray crystallographic studies of the ansa products [(4a), (5a), (6a) and (7a)] have provided definitive proof of the cis-directing effect of the P-NHR moiety in cyclotriphosphazenes. It is likely that hydrogen-bond interaction between the incoming nucleophile and the P-NHR moiety of the reactant accounts for the preference for products with the substituents cis to the NH group. (C) 2009 Elsevier B.V. All rights reserved.
773-777
Beşli, Serap
63ec1cf4-d0d6-4982-9e0a-c632f1f98d08
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Davies, David B.
675b90e6-0c3c-468b-9996-326220517cc6
Kılıç, Adem
565a42ec-2d18-4142-8b37-bb74b244b2f5
Okutan, Elif
962b5f3a-09d5-417f-89df-39ba9a3be3f5
Shaw, Robert A.
a9ecde60-6fe9-4b5d-86e3-77cd5dcfaab8
Tanrıverdi, Esra
806ea1c6-3e7a-4f54-88e1-ce5ba4d40745
Çiftçi, Gönül Yenilmez
ec263230-06cb-46be-b546-f366b4a38438
Beşli, Serap
63ec1cf4-d0d6-4982-9e0a-c632f1f98d08
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Davies, David B.
675b90e6-0c3c-468b-9996-326220517cc6
Kılıç, Adem
565a42ec-2d18-4142-8b37-bb74b244b2f5
Okutan, Elif
962b5f3a-09d5-417f-89df-39ba9a3be3f5
Shaw, Robert A.
a9ecde60-6fe9-4b5d-86e3-77cd5dcfaab8
Tanrıverdi, Esra
806ea1c6-3e7a-4f54-88e1-ce5ba4d40745
Çiftçi, Gönül Yenilmez
ec263230-06cb-46be-b546-f366b4a38438

Beşli, Serap, Coles, Simon J., Davies, David B., Kılıç, Adem, Okutan, Elif, Shaw, Robert A., Tanrıverdi, Esra and Çiftçi, Gönül Yenilmez (2009) A cis-directing effect towards diols by an exocyclic P-NHR moiety in cyclotriphosphazenes. Inorganic Chemistry Communications, 12 (8), 773-777. (doi:10.1016/j.inoche.2009.06.014).

Record type: Article

Abstract

Cyclophosphazenes containing the P-NHR moiety in an exocyclic spiro ring, N(3)P(3)Cl(4)[NH(CH(2))(3)O], (1), and N(3)P(3)Cl(4)[NH(CH(2))(3)NMe], (2). were used to investigate a possible directing effect of the P-NHR moiety oil the formation of products in the nucleophilic substitution reactions with diols Such as tetraethyleneglycol, 1,3-propanediol and 2,2-dimetliyl-1,3-propanediol. The (31)P NMR spectra of the reaction Mixtures showed that only one kind of ansa product is formed in each of these reactions. X-ray crystallographic studies of the ansa products [(4a), (5a), (6a) and (7a)] have provided definitive proof of the cis-directing effect of the P-NHR moiety in cyclotriphosphazenes. It is likely that hydrogen-bond interaction between the incoming nucleophile and the P-NHR moiety of the reactant accounts for the preference for products with the substituents cis to the NH group. (C) 2009 Elsevier B.V. All rights reserved.

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Published date: August 2009
Organisations: Organic Chemistry: Synthesis, Catalysis and Flow

Identifiers

Local EPrints ID: 346347
URI: https://eprints.soton.ac.uk/id/eprint/346347
PURE UUID: ad4c455f-5323-4e5e-bfd4-be4f93103a07
ORCID for Simon J. Coles: ORCID iD orcid.org/0000-0001-8414-9272

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Date deposited: 20 Dec 2012 15:25
Last modified: 29 Oct 2019 01:58

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