Computer-Assisted Design and Synthetic Applications of Chiral Enol Borinates: Novel, Highly Enantioselective Aldol Reagents
We have recently described the development of a quantitative transition state model for the prediction of stereoselectivity in the boron-mediated aldol reaction. This model provides qualitative insights into the factors contributing to the stereochemical outcome of a variety of reactions of syntheti...
| Main Authors: | , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
Sociedade Brasileira de Química
1998-01-01
|
| Series: | Journal of the Brazilian Chemical Society |
| Subjects: | |
| Online Access: | http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50531998000400004 |
| _version_ | 1811343748375773184 |
|---|---|
| author | Gennari Cesare Ceccarelli Simona Piarulli Umberto Aboutayab Karim |
| author_facet | Gennari Cesare Ceccarelli Simona Piarulli Umberto Aboutayab Karim |
| author_sort | Gennari Cesare |
| collection | DOAJ |
| description | We have recently described the development of a quantitative transition state model for the prediction of stereoselectivity in the boron-mediated aldol reaction. This model provides qualitative insights into the factors contributing to the stereochemical outcome of a variety of reactions of synthetic importance. The force field model was used to assist the design and preparation of new chiral boron ligands derived from menthone. The chiral boron enolates were employed in various stereoselective processes, including the addition to chiral aldehydes and the reagent-controlled total synthesis of (3S,4S)-statine. The chiral enolates derived from alpha-halo and alpha-oxysubstituted thioacetates were added to aldehydes and imines. Addition to imines leads to the enantioselective synthesis of chiral aziridines, a formal total synthesis of (+)-thiamphenicol, and a new highly efficient synthesis of the paclitaxel (taxol®) C-13 side-chain and taxol semisynthesis from baccatin III. The stereochemical outcome of the addition to imines was rationalised with the aid of computational studies. Enantioselective addition reactions of the chiral boron enolate derived from thioacetate have successfully been applied to solid phase bound aldehydes to give aldol products in comparable yields and enantioselectivities to the usual solution conditions. |
| first_indexed | 2024-04-13T19:35:20Z |
| format | Article |
| id | doaj.art-4acefa65b7a746fbb8ba0905a9c8920f |
| institution | Directory Open Access Journal |
| issn | 0103-5053 |
| language | English |
| last_indexed | 2024-04-13T19:35:20Z |
| publishDate | 1998-01-01 |
| publisher | Sociedade Brasileira de Química |
| record_format | Article |
| series | Journal of the Brazilian Chemical Society |
| spelling | doaj.art-4acefa65b7a746fbb8ba0905a9c8920f2022-12-22T02:33:03ZengSociedade Brasileira de QuímicaJournal of the Brazilian Chemical Society0103-50531998-01-0194319326Computer-Assisted Design and Synthetic Applications of Chiral Enol Borinates: Novel, Highly Enantioselective Aldol ReagentsGennari CesareCeccarelli SimonaPiarulli UmbertoAboutayab KarimWe have recently described the development of a quantitative transition state model for the prediction of stereoselectivity in the boron-mediated aldol reaction. This model provides qualitative insights into the factors contributing to the stereochemical outcome of a variety of reactions of synthetic importance. The force field model was used to assist the design and preparation of new chiral boron ligands derived from menthone. The chiral boron enolates were employed in various stereoselective processes, including the addition to chiral aldehydes and the reagent-controlled total synthesis of (3S,4S)-statine. The chiral enolates derived from alpha-halo and alpha-oxysubstituted thioacetates were added to aldehydes and imines. Addition to imines leads to the enantioselective synthesis of chiral aziridines, a formal total synthesis of (+)-thiamphenicol, and a new highly efficient synthesis of the paclitaxel (taxol®) C-13 side-chain and taxol semisynthesis from baccatin III. The stereochemical outcome of the addition to imines was rationalised with the aid of computational studies. Enantioselective addition reactions of the chiral boron enolate derived from thioacetate have successfully been applied to solid phase bound aldehydes to give aldol products in comparable yields and enantioselectivities to the usual solution conditions.http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50531998000400004chiral boron enolatesenantioselective aldol reactionsstatinepaclitaxel |
| spellingShingle | Gennari Cesare Ceccarelli Simona Piarulli Umberto Aboutayab Karim Computer-Assisted Design and Synthetic Applications of Chiral Enol Borinates: Novel, Highly Enantioselective Aldol Reagents Journal of the Brazilian Chemical Society chiral boron enolates enantioselective aldol reactions statine paclitaxel |
| title | Computer-Assisted Design and Synthetic Applications of Chiral Enol Borinates: Novel, Highly Enantioselective Aldol Reagents |
| title_full | Computer-Assisted Design and Synthetic Applications of Chiral Enol Borinates: Novel, Highly Enantioselective Aldol Reagents |
| title_fullStr | Computer-Assisted Design and Synthetic Applications of Chiral Enol Borinates: Novel, Highly Enantioselective Aldol Reagents |
| title_full_unstemmed | Computer-Assisted Design and Synthetic Applications of Chiral Enol Borinates: Novel, Highly Enantioselective Aldol Reagents |
| title_short | Computer-Assisted Design and Synthetic Applications of Chiral Enol Borinates: Novel, Highly Enantioselective Aldol Reagents |
| title_sort | computer assisted design and synthetic applications of chiral enol borinates novel highly enantioselective aldol reagents |
| topic | chiral boron enolates enantioselective aldol reactions statine paclitaxel |
| url | http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50531998000400004 |
| work_keys_str_mv | AT gennaricesare computerassisteddesignandsyntheticapplicationsofchiralenolborinatesnovelhighlyenantioselectivealdolreagents AT ceccarellisimona computerassisteddesignandsyntheticapplicationsofchiralenolborinatesnovelhighlyenantioselectivealdolreagents AT piarulliumberto computerassisteddesignandsyntheticapplicationsofchiralenolborinatesnovelhighlyenantioselectivealdolreagents AT aboutayabkarim computerassisteddesignandsyntheticapplicationsofchiralenolborinatesnovelhighlyenantioselectivealdolreagents |