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...
| Authors: | ; ; ; |
|---|---|
| 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 |
| _version_ | 1878731358634770433 |
|---|---|
| author | Sedano Labrador, Carlos |
| author2 | Virumbrales Ortiz, Cintia Suarez Pantiga, Samuel Sanz Díez, Roberto |
| author2_role | author author author |
| author_browse | Sanz Díez, Roberto Sedano Labrador, Carlos Suarez Pantiga, Samuel Virumbrales Ortiz, Cintia |
| author_facet | Sedano Labrador, Carlos Virumbrales Ortiz, Cintia Suarez Pantiga, Samuel Sanz Díez, Roberto |
| author_role | author |
| collection | Repositorio Institucional de la Universidad de Burgos (RIUBU) |
| 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. |
| eu_rights_str_mv | openAccess |
| format | article |
| id | ES_2dfdb187b9e82953d844629db2e4eab2 |
| institution | Universidad de Burgos (UBU) |
| instname_str | Universidad de Burgos (UBU) |
| network_acronym_str | ES |
| network_name_str | España |
| oai_identifier_str | oai:riubu.ubu.es:10259/6089 |
| publishDate | 2021 |
| publishDateSort | 2021 |
| publisher | Thieme |
| publisherStr | Thieme |
| reponame_str | Repositorio Institucional de la Universidad de Burgos (RIUBU) |
| spelling | Aldol–Tishchenko Reaction of α-Oxy Ketones: Diastereoselective Synthesis of 1,2,3-Triol Derivatives Sedano Labrador, Carlos Virumbrales Ortiz, Cintia Suarez Pantiga, Samuel Sanz Díez, Roberto aldol–Tishchenko reaction enolates α-oxy ketones polyol derivatives diastereoselectivity oxetanes Química orgánica Chemistry, Organic 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 Thieme http://hdl.handle.net/10259/6089 |
| 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 |
| status_str | acceptedVersion |
| title | 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_short | 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 |
| topic | aldol–Tishchenko reaction enolates α-oxy ketones polyol derivatives diastereoselectivity oxetanes Química orgánica Chemistry, Organic |
| topic_facet | aldol–Tishchenko reaction enolates α-oxy ketones polyol derivatives diastereoselectivity oxetanes Química orgánica Chemistry, Organic |
| url | http://hdl.handle.net/10259/6089 |