General quantum-based NMR method for the assignment of absolute configuration by single or double derivatization : scope and limitations

Abstract: The determination of the absolute configuration of chiral alcohols and amines is typically carried out with modified Mosher methods involving a double-derivatization strategy. On the other hand, the number of robust and reliable methods to accomplish that goal using a single derivatization...

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Autores principales: Zanardi, María Marta, Biglione, Franco Agustín, Sortino, Maximiliano A., Sarotti, Ariel Marcelo
Formato: Artículo
Lenguaje:Inglés
Publicado: American Chemical Society 2019
Materias:
RESONANCIA NUCLEAR MAGNETICA
QUIMICA ORGANICA
Acceso en línea:https://repositorio.uca.edu.ar/handle/123456789/8669
Aporte de:
Repositorio Institucional de la Universidad Católica Argentina (UCA) de Universidad Católica Argentina
id I33-R139123456789-8669
record_format dspace
institution Universidad Católica Argentina
institution_str I-33
repository_str R-139
collection Repositorio Institucional de la Universidad Católica Argentina (UCA)
language Inglés
topic RESONANCIA NUCLEAR MAGNETICA
QUIMICA ORGANICA
spellingShingle RESONANCIA NUCLEAR MAGNETICA
QUIMICA ORGANICA
Zanardi, María Marta
Biglione, Franco Agustín
Sortino, Maximiliano A.
Sarotti, Ariel Marcelo
General quantum-based NMR method for the assignment of absolute configuration by single or double derivatization : scope and limitations
topic_facet RESONANCIA NUCLEAR MAGNETICA
QUIMICA ORGANICA
description Abstract: The determination of the absolute configuration of chiral alcohols and amines is typically carried out with modified Mosher methods involving a double-derivatization strategy. On the other hand, the number of robust and reliable methods to accomplish that goal using a single derivatization approach is much less abundant and mainly limited to secondary alcohols or primary amines. Herein, we report a conceptually novel strategy to settle the most likely absolute configuration of a wide variety of substrates and chiral derivatizing agents following a single-derivatization experiment coupled with quantum calculations of NMR shifts and DP4+ analysis. Using an ambitious set of 114 examples, our methodology succeeded in setting the correct absolute configuration of the substrates in 96% of the cases. The classification achieved with secondary alcohols, secondary amines, and primary amines herein studied was excellent (100%), whereas more modest results (89%) were observed for primary and tertiary alcohols. Moreover, a new DP4+ integrated probability was built to strengthen the analysis when the NMR data of the two possible diastereoisomers are available. The suitability of these methods in solving the absolute configuration of two relevant cases of stereochemical misassignment ((+)- erythro-mefloquine and angiopterlactone B) is also provided.
format Artículo
author Zanardi, María Marta
Biglione, Franco Agustín
Sortino, Maximiliano A.
Sarotti, Ariel Marcelo
author_facet Zanardi, María Marta
Biglione, Franco Agustín
Sortino, Maximiliano A.
Sarotti, Ariel Marcelo
author_sort Zanardi, María Marta
title General quantum-based NMR method for the assignment of absolute configuration by single or double derivatization : scope and limitations
title_short General quantum-based NMR method for the assignment of absolute configuration by single or double derivatization : scope and limitations
title_full General quantum-based NMR method for the assignment of absolute configuration by single or double derivatization : scope and limitations
title_fullStr General quantum-based NMR method for the assignment of absolute configuration by single or double derivatization : scope and limitations
title_full_unstemmed General quantum-based NMR method for the assignment of absolute configuration by single or double derivatization : scope and limitations
title_sort general quantum-based nmr method for the assignment of absolute configuration by single or double derivatization : scope and limitations
publisher American Chemical Society
publishDate 2019
url https://repositorio.uca.edu.ar/handle/123456789/8669
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