An unusual epimerization of a thioether

Woo Jin Chung; Ganga Viswanathan Bhagavathy; Neil E. Jacobsen; Stephanie Senef; Richard S. Glass

doi:10.1080/17415993.2012.714783

An unusual epimerization of a thioether

Woo Jin Chung, Ganga Viswanathan Bhagavathy, Neil E. Jacobsen, Stephanie Senef, Richard S. Glass

Research output: Contribution to journal › Article › peer-review

Abstract

Reaction of 6-exo-methylthio-2-exo-phenylbicyclo[2.2.1]heptan-2-endo-ol with sodium azide and acid afforded the corresponding 2-exo-azide. This azide was reduced and acetylated to give a crystalline derivative whose structure was unequivocally established by X-ray crystallographic analysis. Surprisingly, the isomeric 6-endo-methylthio-2-exo-phenylbicyclo[2.2.1]heptan-2-endo-ol on reaction with sodium azide and acid yielded the same azide as the 6-exo-methylthio analogue. Evidence for the mechanism of thioisomerization is presented.

Original language	English (US)
Pages (from-to)	67-78
Number of pages	12
Journal	Journal of Sulfur Chemistry
Volume	34
Issue number	1-2
DOIs	https://doi.org/10.1080/17415993.2012.714783
State	Published - Apr 1 2013
Externally published	Yes

Keywords

endo - exo rearrangement
norbornyl

ASJC Scopus subject areas

General Chemistry

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10.1080/17415993.2012.714783

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title = "An unusual epimerization of a thioether",

abstract = "Reaction of 6-exo-methylthio-2-exo-phenylbicyclo[2.2.1]heptan-2-endo-ol with sodium azide and acid afforded the corresponding 2-exo-azide. This azide was reduced and acetylated to give a crystalline derivative whose structure was unequivocally established by X-ray crystallographic analysis. Surprisingly, the isomeric 6-endo-methylthio-2-exo-phenylbicyclo[2.2.1]heptan-2-endo-ol on reaction with sodium azide and acid yielded the same azide as the 6-exo-methylthio analogue. Evidence for the mechanism of thioisomerization is presented.",

keywords = "endo - exo rearrangement, norbornyl",

author = "Chung, {Woo Jin} and Bhagavathy, {Ganga Viswanathan} and Jacobsen, {Neil E.} and Stephanie Senef and Glass, {Richard S.}",

note = "Funding Information: We thank the National Science Foundation for financial support of this research (CHE-0455575 and CHE-0956581). The crystallographic data for 9 were collected by Dr Allen G. Oliver and Dr Jeanette A. Krause through SCrALS at the Advanced Light Source which is supported by the U.S. Department of Energy, Office of Energy Sciences, Materials Science Division under contract DE-AC02-05CH11231 at Lawrence Berkeley National Laboratory.",

year = "2013",

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doi = "10.1080/17415993.2012.714783",

language = "English (US)",

volume = "34",

pages = "67--78",

journal = "Journal of Sulfur Chemistry",

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T1 - An unusual epimerization of a thioether

AU - Chung, Woo Jin

AU - Bhagavathy, Ganga Viswanathan

AU - Jacobsen, Neil E.

AU - Senef, Stephanie

AU - Glass, Richard S.

N1 - Funding Information: We thank the National Science Foundation for financial support of this research (CHE-0455575 and CHE-0956581). The crystallographic data for 9 were collected by Dr Allen G. Oliver and Dr Jeanette A. Krause through SCrALS at the Advanced Light Source which is supported by the U.S. Department of Energy, Office of Energy Sciences, Materials Science Division under contract DE-AC02-05CH11231 at Lawrence Berkeley National Laboratory.

PY - 2013/4/1

Y1 - 2013/4/1

N2 - Reaction of 6-exo-methylthio-2-exo-phenylbicyclo[2.2.1]heptan-2-endo-ol with sodium azide and acid afforded the corresponding 2-exo-azide. This azide was reduced and acetylated to give a crystalline derivative whose structure was unequivocally established by X-ray crystallographic analysis. Surprisingly, the isomeric 6-endo-methylthio-2-exo-phenylbicyclo[2.2.1]heptan-2-endo-ol on reaction with sodium azide and acid yielded the same azide as the 6-exo-methylthio analogue. Evidence for the mechanism of thioisomerization is presented.

AB - Reaction of 6-exo-methylthio-2-exo-phenylbicyclo[2.2.1]heptan-2-endo-ol with sodium azide and acid afforded the corresponding 2-exo-azide. This azide was reduced and acetylated to give a crystalline derivative whose structure was unequivocally established by X-ray crystallographic analysis. Surprisingly, the isomeric 6-endo-methylthio-2-exo-phenylbicyclo[2.2.1]heptan-2-endo-ol on reaction with sodium azide and acid yielded the same azide as the 6-exo-methylthio analogue. Evidence for the mechanism of thioisomerization is presented.

KW - endo - exo rearrangement

KW - norbornyl

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ER -

An unusual epimerization of a thioether

Abstract

Keywords

ASJC Scopus subject areas

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