Stereoselective synthesis and determination of the C-16 configuration of 16-halomethyl-16/hydroxymethyl steroids

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Abstract

A considerable stereoselectivity was found during the hydroxy → halogen exchange reaction of 16,16-bis(hydroxymethyl)-17-oxo- and -17-β-hydroxy-3-methoxyestra-1,3,5(10)-trienes depending on the starting materials and on the conditions of the reaction. The 17-oxo steroid 1 is transformed by acetic acid/hydrogen bromide solely into 16β-acetoxymethyl-16α-bromomethyl-3-methoxyestra-1,3,5(10)-trien-17- one (3a). In contrast, the 17β-hydroxy steroid 4 yields a mixture of the two 16-epimers 7a and 8a. The formation of these brominated steroids can be interpreted in terms of front-side neighboring group participation. The hydroxy → halogen exchange of 16,16-bis(hydroxymethyl)-17β-hydroxy compound 4 with carbon tetrachloride or carbon tetrabromide in the presence of triphenylphosphine proceeds stereoselectively, and only the 16β-halomethyl epimers 8a and 8b are formed. Constitutions of the new steroids were proved by IR, 1H and 13C NMR spectra. The C-16 configuration of the epimeric pairs was determined by NOE measurements.

Original languageEnglish
Pages (from-to)1280-1283
Number of pages4
JournalSynthesis
Issue number12
Publication statusPublished - 1992

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Stereoselectivity
Carbon tetrachloride
Acetic acid
Ion exchange
Brominated Steroids
Halogens
Steroids
Nuclear magnetic resonance
Hydrogen
Carbon
Hydrobromic Acid
Trientine
Carbon Tetrachloride
Acetic Acid

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

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title = "Stereoselective synthesis and determination of the C-16 configuration of 16-halomethyl-16/hydroxymethyl steroids",
abstract = "A considerable stereoselectivity was found during the hydroxy → halogen exchange reaction of 16,16-bis(hydroxymethyl)-17-oxo- and -17-β-hydroxy-3-methoxyestra-1,3,5(10)-trienes depending on the starting materials and on the conditions of the reaction. The 17-oxo steroid 1 is transformed by acetic acid/hydrogen bromide solely into 16β-acetoxymethyl-16α-bromomethyl-3-methoxyestra-1,3,5(10)-trien-17- one (3a). In contrast, the 17β-hydroxy steroid 4 yields a mixture of the two 16-epimers 7a and 8a. The formation of these brominated steroids can be interpreted in terms of front-side neighboring group participation. The hydroxy → halogen exchange of 16,16-bis(hydroxymethyl)-17β-hydroxy compound 4 with carbon tetrachloride or carbon tetrabromide in the presence of triphenylphosphine proceeds stereoselectively, and only the 16β-halomethyl epimers 8a and 8b are formed. Constitutions of the new steroids were proved by IR, 1H and 13C NMR spectra. The C-16 configuration of the epimeric pairs was determined by NOE measurements.",
author = "P. Soh{\'a}r and A. Furjes and J. W{\"o}lfling and G. Schneider",
year = "1992",
language = "English",
pages = "1280--1283",
journal = "Synthesis",
issn = "0039-7881",
publisher = "Georg Thieme Verlag",
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TY - JOUR

T1 - Stereoselective synthesis and determination of the C-16 configuration of 16-halomethyl-16/hydroxymethyl steroids

AU - Sohár, P.

AU - Furjes, A.

AU - Wölfling, J.

AU - Schneider, G.

PY - 1992

Y1 - 1992

N2 - A considerable stereoselectivity was found during the hydroxy → halogen exchange reaction of 16,16-bis(hydroxymethyl)-17-oxo- and -17-β-hydroxy-3-methoxyestra-1,3,5(10)-trienes depending on the starting materials and on the conditions of the reaction. The 17-oxo steroid 1 is transformed by acetic acid/hydrogen bromide solely into 16β-acetoxymethyl-16α-bromomethyl-3-methoxyestra-1,3,5(10)-trien-17- one (3a). In contrast, the 17β-hydroxy steroid 4 yields a mixture of the two 16-epimers 7a and 8a. The formation of these brominated steroids can be interpreted in terms of front-side neighboring group participation. The hydroxy → halogen exchange of 16,16-bis(hydroxymethyl)-17β-hydroxy compound 4 with carbon tetrachloride or carbon tetrabromide in the presence of triphenylphosphine proceeds stereoselectively, and only the 16β-halomethyl epimers 8a and 8b are formed. Constitutions of the new steroids were proved by IR, 1H and 13C NMR spectra. The C-16 configuration of the epimeric pairs was determined by NOE measurements.

AB - A considerable stereoselectivity was found during the hydroxy → halogen exchange reaction of 16,16-bis(hydroxymethyl)-17-oxo- and -17-β-hydroxy-3-methoxyestra-1,3,5(10)-trienes depending on the starting materials and on the conditions of the reaction. The 17-oxo steroid 1 is transformed by acetic acid/hydrogen bromide solely into 16β-acetoxymethyl-16α-bromomethyl-3-methoxyestra-1,3,5(10)-trien-17- one (3a). In contrast, the 17β-hydroxy steroid 4 yields a mixture of the two 16-epimers 7a and 8a. The formation of these brominated steroids can be interpreted in terms of front-side neighboring group participation. The hydroxy → halogen exchange of 16,16-bis(hydroxymethyl)-17β-hydroxy compound 4 with carbon tetrachloride or carbon tetrabromide in the presence of triphenylphosphine proceeds stereoselectively, and only the 16β-halomethyl epimers 8a and 8b are formed. Constitutions of the new steroids were proved by IR, 1H and 13C NMR spectra. The C-16 configuration of the epimeric pairs was determined by NOE measurements.

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