Stereoselective deconjugation of macrocyclic α,β-unsaturated esters by sequential amidation and olefin transposition: application to enantioselective phase transfer catalysis
| Autor: | Mahesh Vishe, Laure Guénée, Alexandre Homberg, Radim Hrdina, Jérôme Lacour |
|---|---|
| Jazyk: | angličtina |
| Rok vydání: | 2019 |
| Předmět: |
Olefin fiber
010405 organic chemistry Chemistry Stereochemistry Organic Chemistry Enantioselective synthesis Diastereomer 010402 general chemistry 01 natural sciences Biochemistry 0104 chemical sciences chemistry.chemical_compound Enantiopure drug Amide ddc:540 Stereoselectivity Physical and Theoretical Chemistry Guanidine Phenylalanine analog |
| Zdroj: | Organic and Biomolecular Chemistry, Vol. 17, No 28 (2019) pp. 6905-6910 |
| ISSN: | 1477-0520 |
| Popis: | The stereoselective synthesis of chiral macrocycles bearing two aliphatic amide functional groups is reported. After the amidation mediated by TBD, a guanidine derivative, the olefin transposition step is performed with a slight excess of t-BuOK. The products are afforded in moderate to good combined yields (up to 59%) and with an excellent syn diastereoselectivity (dr > 49 : 1). Introducing enantiopure α-branched substituents was possible and it resulted in mixtures of diastereomers, which could be tested as phase-transfer catalysts using the formation of a phenylalanine analog as a test reaction (up to 43% ee). A clear matched–mismatched situation was observed in the two diastereomeric series. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|