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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...

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Autores principales: Turlik, Aneta, Ando, Kaori, Mackey, Pamela, Alcock, Emma, Light, Mark, McGlacken, Gerard P., Houk, K. N.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2021
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.
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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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