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Sulfimidation of thioether groups - a versatile method for modifying and linking thia/oxa crowns

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posted on 20.08.2014, 10:28 authored by Mark ElsegoodMark Elsegood, Paul KellyPaul Kelly, Gillian Reid, Alexandra M.Z. Slawin, Paul M. Staniland
Reaction of the mixed thioether/ether crowns [9]aneO2S 1, [12]aneO3S 2 and [18]aneO4S23 with one mol. equivalent of the aminating agent MSH (o-mesitylsulfonylhydroxylamine) in Et2O results in the formation of the mono-sulfimidated systems {[9]aneO2(S[double bond, length as m-dash]NH2)}+1a, {[12]aneO3(S[double bond, length as m-dash]NH2)}+2a and {[18]aneO4S(S[double bond, length as m-dash]NH2)}+3a, while using two mol. equivalents of MSH with 3 gives the disulfimidium cation {[18]aneO4(S[double bond, length as m-dash]NH2)2}2+3b. All of these species have been isolated in good yields as the [mesSO3]− (mes = 2,4,6-Me3C6H2) salts and can be readily converted to the [BPh4]− salts by metathesis with Na[BPh4]. Treatment of 1a or 2a with lithium diisopropylamide (LDA) and N-bromosuccinimide (NBS) at −78 °C, followed by addition of a further equivalent of the parent thia/oxa crown, gives monocationic N-bridged sulfimide bicyclic compounds (4 and 5 respectively), in which the crowns are linked by the sulfimidic nitrogen. Reaction of 3a with LDA and NBS leads to formation of the {([18]aneO4S2)N}+ cation 6 which exhibits an intramolecular S–N–S bridge. Crystallographic studies on representative examples of each compound type are described, together with their spectroscopic properties.

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School

  • Science

Department

  • Chemistry

Published in

DALTON TRANSACTIONS

Issue

37

Pages

5076 - 5082 (7)

Citation

ELSEGOOD, M.R.J., KELLY, P.F., REID, G. ... et al., 2008. Sulfimidation of thioether groups - a versatile method for modifying and linking thia/oxa crowns. Dalton Transactions, 37, pp. 5076 - 5082.

Publisher

© The Royal Society of Chemistry

Version

AM (Accepted Manuscript)

Publisher statement

This work is made available according to the conditions of the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0) licence. Full details of this licence are available at: https://creativecommons.org/licenses/by-nc-nd/4.0/

Publication date

2008

Notes

This article was published in the journal, Dalton Transactions [© Royal Society of Chemistry] and the definitive version is available at: http://dx.doi.org/10.1039/b802903b

ISSN

1477-9226

Language

en

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