Aldol–Tishchenko Reaction of α-Oxy Ketones: Diastereoselective Synthesis of 1,2,3-Triol Derivatives

α-Oxy ketones, easily accessible by conventional routes, can be selectively deprotonated generating an enolate intermediate, which upon treatment with paraformaldehyde undergoes an aldol–Tishchenko reaction, leading to relevant 1,2,3-triol fragments in a totally diastereoselective manner. The excell...

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Autores: Sedano Labrador, Carlos, Virumbrales Ortiz, Cintia, Suarez Pantiga, Samuel, Sanz Díez, Roberto
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2021
País:España
Institución:Universidad de Burgos (UBU)
Repositorio:Repositorio Institucional de la Universidad de Burgos (RIUBU)
OAI Identifier:oai:riubu.ubu.es:10259/6089
Acceso en línea:http://hdl.handle.net/10259/6089
Access Level:acceso abierto
Palabra clave:aldol–Tishchenko reaction
enolates
α-oxy ketones
polyol derivatives
diastereoselectivity
oxetanes
Química orgánica
Chemistry, Organic
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spelling Aldol–Tishchenko Reaction of α-Oxy Ketones: Diastereoselective Synthesis of 1,2,3-Triol DerivativesSedano Labrador, CarlosVirumbrales Ortiz, CintiaSuarez Pantiga, SamuelSanz Díez, Robertoaldol–Tishchenko reactionenolatesα-oxy ketonespolyol derivativesdiastereoselectivityoxetanesQuímica orgánicaChemistry, Organicα-Oxy ketones, easily accessible by conventional routes, can be selectively deprotonated generating an enolate intermediate, which upon treatment with paraformaldehyde undergoes an aldol–Tishchenko reaction, leading to relevant 1,2,3-triol fragments in a totally diastereoselective manner. The excellent stereocontrol in the generation of a quaternary stereocenter is attributed to stereoelectronic effects in the Evans intermediate. This methodology allows overcoming some limitations of our previously reported strategy, based on the reaction of α-lithiobenzyl ethers with esters and paraformaldehyde, broadening the scope of the obtained polyols. Synthetic applications of this process include the preparation of a new dilignol model and some functionalized oxetanes.Ministerio de Ciencia e Innovación and FEDER (CTQ2016-75023-C2-1-P), and Junta de Castilla y León and FEDER (BU291P18, BU049P20). The project leading to these results has also received funding from the “la Caixa” Foundation, under agreement LCF/PR/PR18/51130007) (CAIXA-UBU001). A postdoctoral contract (S.S.-P.) and a predoctoral contract (C.S.) were funded by Junta de Castilla y León and FEDER and Ministerio de Educación (FPU), respectivelyThieme202120212021info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersionapplication/pdfhttp://hdl.handle.net/10259/6089reponame:Repositorio Institucional de la Universidad de Burgos (RIUBU)instname:Universidad de Burgos (UBU)InglésSynthesis. 2021, V. 53, n. 20, p. 3725-3734https://doi.org/10.1055/a-1509-5655info:eu-repo/semantics/openAccessoai:riubu.ubu.es:10259/60892026-05-28T07:56:11Z
dc.title.none.fl_str_mv Aldol–Tishchenko Reaction of α-Oxy Ketones: Diastereoselective Synthesis of 1,2,3-Triol Derivatives
title Aldol–Tishchenko Reaction of α-Oxy Ketones: Diastereoselective Synthesis of 1,2,3-Triol Derivatives
spellingShingle Aldol–Tishchenko Reaction of α-Oxy Ketones: Diastereoselective Synthesis of 1,2,3-Triol Derivatives
Sedano Labrador, Carlos
aldol–Tishchenko reaction
enolates
α-oxy ketones
polyol derivatives
diastereoselectivity
oxetanes
Química orgánica
Chemistry, Organic
title_short Aldol–Tishchenko Reaction of α-Oxy Ketones: Diastereoselective Synthesis of 1,2,3-Triol Derivatives
title_full Aldol–Tishchenko Reaction of α-Oxy Ketones: Diastereoselective Synthesis of 1,2,3-Triol Derivatives
title_fullStr Aldol–Tishchenko Reaction of α-Oxy Ketones: Diastereoselective Synthesis of 1,2,3-Triol Derivatives
title_full_unstemmed Aldol–Tishchenko Reaction of α-Oxy Ketones: Diastereoselective Synthesis of 1,2,3-Triol Derivatives
title_sort Aldol–Tishchenko Reaction of α-Oxy Ketones: Diastereoselective Synthesis of 1,2,3-Triol Derivatives
dc.creator.none.fl_str_mv Sedano Labrador, Carlos
Virumbrales Ortiz, Cintia
Suarez Pantiga, Samuel
Sanz Díez, Roberto
author Sedano Labrador, Carlos
author_facet Sedano Labrador, Carlos
Virumbrales Ortiz, Cintia
Suarez Pantiga, Samuel
Sanz Díez, Roberto
author_role author
author2 Virumbrales Ortiz, Cintia
Suarez Pantiga, Samuel
Sanz Díez, Roberto
author2_role author
author
author
dc.subject.none.fl_str_mv aldol–Tishchenko reaction
enolates
α-oxy ketones
polyol derivatives
diastereoselectivity
oxetanes
Química orgánica
Chemistry, Organic
topic aldol–Tishchenko reaction
enolates
α-oxy ketones
polyol derivatives
diastereoselectivity
oxetanes
Química orgánica
Chemistry, Organic
description α-Oxy ketones, easily accessible by conventional routes, can be selectively deprotonated generating an enolate intermediate, which upon treatment with paraformaldehyde undergoes an aldol–Tishchenko reaction, leading to relevant 1,2,3-triol fragments in a totally diastereoselective manner. The excellent stereocontrol in the generation of a quaternary stereocenter is attributed to stereoelectronic effects in the Evans intermediate. This methodology allows overcoming some limitations of our previously reported strategy, based on the reaction of α-lithiobenzyl ethers with esters and paraformaldehyde, broadening the scope of the obtained polyols. Synthetic applications of this process include the preparation of a new dilignol model and some functionalized oxetanes.
publishDate 2021
dc.date.none.fl_str_mv 2021
2021
2021
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/acceptedVersion
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10259/6089
url http://hdl.handle.net/10259/6089
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv Synthesis. 2021, V. 53, n. 20, p. 3725-3734
https://doi.org/10.1055/a-1509-5655
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Thieme
publisher.none.fl_str_mv Thieme
dc.source.none.fl_str_mv reponame:Repositorio Institucional de la Universidad de Burgos (RIUBU)
instname:Universidad de Burgos (UBU)
instname_str Universidad de Burgos (UBU)
reponame_str Repositorio Institucional de la Universidad de Burgos (RIUBU)
collection Repositorio Institucional de la Universidad de Burgos (RIUBU)
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,300724

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