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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Bibliographic Details
Authors: Sedano Labrador, Carlos; Virumbrales Ortiz, Cintia; Suarez Pantiga, Samuel; Sanz Díez, Roberto
Format: Article
Status:Accepted version
Publication date:2021
Country:España
Institution:Universidad de Burgos (UBU)
Repository:Repositorio Institucional de la Universidad de Burgos (RIUBU)
OAI Identifier:oai:riubu.ubu.es:10259/6089
Online Access:http://hdl.handle.net/10259/6089
Access Level:Open access
Keyword:aldol–Tishchenko reaction
enolates
α-oxy ketones
polyol derivatives
diastereoselectivity
oxetanes
Química orgánica
Chemistry, Organic
Description
Summary: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.