2026-09-06T17:23:42Zhttps://riubu.ubu.es/oai/request

oai:riubu.ubu.es:10259/60892022-10-31T23:42:08Zcom_10259_3593com_10259_5086com_10259_2604col_10259_3594

Sedano Labrador, Carlos Virumbrales Ortiz, Cintia Suarez Pantiga, Samuel Sanz Díez, Roberto 2021-11-04T09:23:20Z 2021-11-04T09:23:20Z 2021-10 0039-7881 http://hdl.handle.net/10259/6089 10.1055/a-1509-5655 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. 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), respectively application/pdf eng Thieme Synthesis. 2021, V. 53, n. 20, p. 3725-3734 https://doi.org/10.1055/a-1509-5655 aldol–Tishchenko reaction enolates α-oxy ketones polyol derivatives diastereoselectivity oxetanes Química orgánica Chemistry, Organic Aldol–Tishchenko Reaction of α-Oxy Ketones: Diastereoselective Synthesis of 1,2,3-Triol Derivatives info:eu-repo/semantics/article info:eu-repo/semantics/acceptedVersion info:eu-repo/semantics/openAccess