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Phosphorus, Sulfur, and Silicon and the Related Elements Volume 185, 2010 - Issue 5-6: A Tribute to the Chemistry of Professor Naomichi Furukawa
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Original Articles

Ring-Opening of NH-Aziridines with Thiols in Ionic Liquids: Application to the Synthesis of Aminosulfide Catalysts for Asymmetric Epoxidation of Aldehydes

Mariam Namutebi School of Chemistry, University of Bristol, Bristol, UK
,
Eoghan M. McGarrigle School of Chemistry, University of Bristol, Bristol, UK
&
Varinder K. Aggarwal School of Chemistry, University of Bristol, Bristol, UK
Pages 1250-1272 | Received 27 Dec 2008, Accepted 28 Dec 2008, Published online: 27 May 2010
 
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Abstract

The ring opening of NH-aziridines with thiols was found to proceed in good yield at room temperature in the presence of an ionic liquid—1-butyl-3-methylimidazolium chloride (BMIM chloride). This mild methodology was applied to the synthesis of a camphor-derived chiral aminosulfide. The sulfide was used to generate a sulfur ylide, which effected an asymmetric epoxidation of benzaldehyde (e.r. 85:15, trans:cis 90:10, 87% yield). The amino group enabled easy recovery of the sulfide (98% yield) after the reaction by a simple acid/base extraction.

Acknowledgments

Dedicated to Professor Naomichi Furukawa on the occasion of his 70th birthday.

MN acknowledges the University of Bristol for a doctoral training grant. VKA thanks the Royal Society for a Wolfson Research Merit Award, the EPSRC for a Senior Research Fellowship, and Merck for research support. We are grateful to Dr. M. F. Haddow and Dr. J. P. H Charmant for determination of the solid-state structure of compound 11 and 12 by single crystal X-ray diffraction studies, and Dr. Craig Butts for NMR assistance.

Notes

a Isolated yield.

a Isolated yield of aminosulfide.

b dr 1:1.

c 60% unreacted thiol was isolated.

d 50% unreacted thiol was isolated.

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