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

Sulfimidation of thioether groups—a versatile method for modifying and linking thia/oxa crowns
Sulfimidation of thioether groups—a versatile method for modifying and linking thia/oxa crowns
Reaction of the mixed thioether/ether crowns [9]aneO2S 1, [12]aneO3S 2 and [18]aneO4S2 3 with one mol. equivalent of the aminating agent MSH (o-mesitylsulfonylhydroxylamine) in Et2O results in the formation of the mono-sulfimidated systems {[9]aneO2(SNH2)}+ 1a, {[12]aneO3(SNH2)}+ 2a and {[18]aneO4S(SNH2)}+ 3a, while using two mol. equivalents of MSH with 3 gives the disulfimidium cation {[18]aneO4(SNH2)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.
0300-9246
5076-5082
Elsegood, Mark R.J.
cd443b3b-44f9-461c-8310-a885eb86a44e
Kelly, Paul F.
a3668037-0d7a-465a-b258-a907a04e2563
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Slawin, Alexandra M.Z.
45b99a30-c91c-4306-be37-6b7b0ec0affd
Staniland, Paul M.
3238869c-6f12-4b0c-b0ca-3204e28d7fdc
Elsegood, Mark R.J.
cd443b3b-44f9-461c-8310-a885eb86a44e
Kelly, Paul F.
a3668037-0d7a-465a-b258-a907a04e2563
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Slawin, Alexandra M.Z.
45b99a30-c91c-4306-be37-6b7b0ec0affd
Staniland, Paul M.
3238869c-6f12-4b0c-b0ca-3204e28d7fdc

Elsegood, Mark R.J., Kelly, Paul F., Reid, Gillian, Slawin, Alexandra M.Z. and Staniland, Paul M. (2008) Sulfimidation of thioether groups—a versatile method for modifying and linking thia/oxa crowns. Dalton Transactions, 37, 5076-5082. (doi:10.1039/b802903b).

Record type: Article

Abstract

Reaction of the mixed thioether/ether crowns [9]aneO2S 1, [12]aneO3S 2 and [18]aneO4S2 3 with one mol. equivalent of the aminating agent MSH (o-mesitylsulfonylhydroxylamine) in Et2O results in the formation of the mono-sulfimidated systems {[9]aneO2(SNH2)}+ 1a, {[12]aneO3(SNH2)}+ 2a and {[18]aneO4S(SNH2)}+ 3a, while using two mol. equivalents of MSH with 3 gives the disulfimidium cation {[18]aneO4(SNH2)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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Published date: 2008

Identifiers

Local EPrints ID: 146979
URI: http://eprints.soton.ac.uk/id/eprint/146979
ISSN: 0300-9246
PURE UUID: 0a7f156c-1a43-4781-8e29-e33489c18218
ORCID for Gillian Reid: ORCID iD orcid.org/0000-0001-5349-3468

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Date deposited: 23 Apr 2010 08:27
Last modified: 20 Jul 2019 01:21

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