Rearrangement of 18-iodo- and 20-iodopregnanes mediated by iodosyl derivatives

Conversion of 20-acetoxy-18-iodopregn-4-en-3-one 1 to the 18-iodosyl derivative by MCPBA resulted in a Wagner–Meerwein-type rearrangement with regioselective migration of the C13–C17 bond to give, in high yield, an abeo-pregnane in which C-18 was incorporated into ring D. The rearranged steroid was...

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Autores principales:	Nicoletti, D., Ghini, A.A., Baggio, R.F., Garland, M.T., Burton, G.
Formato:	JOUR
Materias:	Chemical bonds Crystal structure Fourier transform infrared spectroscopy Mass spectrometers Nuclear magnetic resonance spectroscopy Positive ions Stereochemistry X ray crystallography Regioselective migration Aromatic hydrocarbons
Acceso en línea:	http://hdl.handle.net/20.500.12110/paper_14727781_v1_n13_p1511_Nicoletti
Aporte de:	Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires

id	todo:paper_14727781_v1_n13_p1511_Nicoletti
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spelling	todo:paper_14727781_v1_n13_p1511_Nicoletti2023-10-03T16:17:59Z Rearrangement of 18-iodo- and 20-iodopregnanes mediated by iodosyl derivatives Nicoletti, D. Ghini, A.A. Baggio, R.F. Garland, M.T. Burton, G. Chemical bonds Crystal structure Fourier transform infrared spectroscopy Mass spectrometers Nuclear magnetic resonance spectroscopy Positive ions Stereochemistry X ray crystallography Regioselective migration Aromatic hydrocarbons Conversion of 20-acetoxy-18-iodopregn-4-en-3-one 1 to the 18-iodosyl derivative by MCPBA resulted in a Wagner–Meerwein-type rearrangement with regioselective migration of the C13–C17 bond to give, in high yield, an abeo-pregnane in which C-18 was incorporated into ring D. The rearranged steroid was epoxidized in situ yielding a mixture of β and α 13,14-epoxides (3 and 4) which were characterized spectroscopically and by X-ray crystallography. When (20R)-20-iodopregn-4-en-3-one 9 was used as substrate, regioselective migration of the C16–C17 bond gave the D-homoandrostane with incorporation of C-20 into ring D in up to 95% yield. The 20S epimer 9 however, gave a mixture of substitution and rearrangement products. The crystal structures of the deacetylated β-epoxide 3 (5), the methanolysis product of α-epoxide 4 (7) and 20-iodopregnanes 9 and 9 are reported. © 2001 The Royal Society of Chemistry. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_14727781_v1_n13_p1511_Nicoletti
institution	Universidad de Buenos Aires
institution_str	I-28
repository_str	R-134
collection	Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
topic	Chemical bonds Crystal structure Fourier transform infrared spectroscopy Mass spectrometers Nuclear magnetic resonance spectroscopy Positive ions Stereochemistry X ray crystallography Regioselective migration Aromatic hydrocarbons
spellingShingle	Chemical bonds Crystal structure Fourier transform infrared spectroscopy Mass spectrometers Nuclear magnetic resonance spectroscopy Positive ions Stereochemistry X ray crystallography Regioselective migration Aromatic hydrocarbons Nicoletti, D. Ghini, A.A. Baggio, R.F. Garland, M.T. Burton, G. Rearrangement of 18-iodo- and 20-iodopregnanes mediated by iodosyl derivatives
topic_facet	Chemical bonds Crystal structure Fourier transform infrared spectroscopy Mass spectrometers Nuclear magnetic resonance spectroscopy Positive ions Stereochemistry X ray crystallography Regioselective migration Aromatic hydrocarbons
description	Conversion of 20-acetoxy-18-iodopregn-4-en-3-one 1 to the 18-iodosyl derivative by MCPBA resulted in a Wagner–Meerwein-type rearrangement with regioselective migration of the C13–C17 bond to give, in high yield, an abeo-pregnane in which C-18 was incorporated into ring D. The rearranged steroid was epoxidized in situ yielding a mixture of β and α 13,14-epoxides (3 and 4) which were characterized spectroscopically and by X-ray crystallography. When (20R)-20-iodopregn-4-en-3-one 9 was used as substrate, regioselective migration of the C16–C17 bond gave the D-homoandrostane with incorporation of C-20 into ring D in up to 95% yield. The 20S epimer 9 however, gave a mixture of substitution and rearrangement products. The crystal structures of the deacetylated β-epoxide 3 (5), the methanolysis product of α-epoxide 4 (7) and 20-iodopregnanes 9 and 9 are reported. © 2001 The Royal Society of Chemistry.
format	JOUR
author	Nicoletti, D. Ghini, A.A. Baggio, R.F. Garland, M.T. Burton, G.
author_facet	Nicoletti, D. Ghini, A.A. Baggio, R.F. Garland, M.T. Burton, G.
author_sort	Nicoletti, D.
title	Rearrangement of 18-iodo- and 20-iodopregnanes mediated by iodosyl derivatives
title_short	Rearrangement of 18-iodo- and 20-iodopregnanes mediated by iodosyl derivatives
title_full	Rearrangement of 18-iodo- and 20-iodopregnanes mediated by iodosyl derivatives
title_fullStr	Rearrangement of 18-iodo- and 20-iodopregnanes mediated by iodosyl derivatives
title_full_unstemmed	Rearrangement of 18-iodo- and 20-iodopregnanes mediated by iodosyl derivatives
title_sort	rearrangement of 18-iodo- and 20-iodopregnanes mediated by iodosyl derivatives
url	http://hdl.handle.net/20.500.12110/paper_14727781_v1_n13_p1511_Nicoletti
work_keys_str_mv	AT nicolettid rearrangementof18iodoand20iodopregnanesmediatedbyiodosylderivatives AT ghiniaa rearrangementof18iodoand20iodopregnanesmediatedbyiodosylderivatives AT baggiorf rearrangementof18iodoand20iodopregnanesmediatedbyiodosylderivatives AT garlandmt rearrangementof18iodoand20iodopregnanesmediatedbyiodosylderivatives AT burtong rearrangementof18iodoand20iodopregnanesmediatedbyiodosylderivatives
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Rearrangement of 18-iodo- and 20-iodopregnanes mediated by iodosyl derivatives

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