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Mechanism and Origins of Stereoselectivity of the Aldol-Tishchenko Reaction of Sulfinimines
[Image: see text] Density functional theory computations have elucidated the mechanism and origins of stereoselectivity in McGlacken’s aldol-Tishchenko reaction for the diastereoselective synthesis of 1,3-amino alcohols using Ellman’s t-butylsulfinimines as chiral auxiliaries. Variations of stereoch...
Autores principales: | , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical
Society
2021
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8279497/ https://www.ncbi.nlm.nih.gov/pubmed/33586983 http://dx.doi.org/10.1021/acs.joc.0c02862 |
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author | Turlik, Aneta Ando, Kaori Mackey, Pamela Alcock, Emma Light, Mark McGlacken, Gerard P. Houk, K. N. |
author_facet | Turlik, Aneta Ando, Kaori Mackey, Pamela Alcock, Emma Light, Mark McGlacken, Gerard P. Houk, K. N. |
author_sort | Turlik, Aneta |
collection | PubMed |
description | [Image: see text] Density functional theory computations have elucidated the mechanism and origins of stereoselectivity in McGlacken’s aldol-Tishchenko reaction for the diastereoselective synthesis of 1,3-amino alcohols using Ellman’s t-butylsulfinimines as chiral auxiliaries. Variations of stereochemical outcome are dependent on the nature of the ketone starting materials used, and the aspects leading to these differences have been rationalized. The intramolecular hydride transfer step is the rate- and stereochemistry-determining step, and all prior steps are reversible. |
format | Online Article Text |
id | pubmed-8279497 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | American Chemical
Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-82794972021-07-15 Mechanism and Origins of Stereoselectivity of the Aldol-Tishchenko Reaction of Sulfinimines Turlik, Aneta Ando, Kaori Mackey, Pamela Alcock, Emma Light, Mark McGlacken, Gerard P. Houk, K. N. J Org Chem [Image: see text] Density functional theory computations have elucidated the mechanism and origins of stereoselectivity in McGlacken’s aldol-Tishchenko reaction for the diastereoselective synthesis of 1,3-amino alcohols using Ellman’s t-butylsulfinimines as chiral auxiliaries. Variations of stereochemical outcome are dependent on the nature of the ketone starting materials used, and the aspects leading to these differences have been rationalized. The intramolecular hydride transfer step is the rate- and stereochemistry-determining step, and all prior steps are reversible. American Chemical Society 2021-02-15 2021-03-05 /pmc/articles/PMC8279497/ /pubmed/33586983 http://dx.doi.org/10.1021/acs.joc.0c02862 Text en © 2021 American Chemical Society Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Turlik, Aneta Ando, Kaori Mackey, Pamela Alcock, Emma Light, Mark McGlacken, Gerard P. Houk, K. N. Mechanism and Origins of Stereoselectivity of the Aldol-Tishchenko Reaction of Sulfinimines |
title | Mechanism and Origins
of Stereoselectivity of the
Aldol-Tishchenko Reaction of Sulfinimines |
title_full | Mechanism and Origins
of Stereoselectivity of the
Aldol-Tishchenko Reaction of Sulfinimines |
title_fullStr | Mechanism and Origins
of Stereoselectivity of the
Aldol-Tishchenko Reaction of Sulfinimines |
title_full_unstemmed | Mechanism and Origins
of Stereoselectivity of the
Aldol-Tishchenko Reaction of Sulfinimines |
title_short | Mechanism and Origins
of Stereoselectivity of the
Aldol-Tishchenko Reaction of Sulfinimines |
title_sort | mechanism and origins
of stereoselectivity of the
aldol-tishchenko reaction of sulfinimines |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8279497/ https://www.ncbi.nlm.nih.gov/pubmed/33586983 http://dx.doi.org/10.1021/acs.joc.0c02862 |
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