Direct Stereoconvergent Allylation of Chiral Alkylcopper Nucleophiles with Racemic Allylic Phosphates
| Autor: | Jung Tae Han, Seoung-Tae Kim, Mu-Hyun Baik, Jaesook Yun |
|---|---|
| Rok vydání: | 2020 |
| Předmět: |
chemistry.chemical_classification
Allylic rearrangement 010405 organic chemistry Organic Chemistry Regioselectivity Homogeneous catalysis General Chemistry 010402 general chemistry 01 natural sciences Medicinal chemistry Catalysis Coupling reaction 0104 chemical sciences chemistry Nucleophile Racemic mixture Moiety Alkyl |
| Zdroj: | Chemistry – A European Journal. 26:2592-2596 |
| ISSN: | 1521-3765 0947-6539 |
| DOI: | 10.1002/chem.201905361 |
| Popis: | Copper-catalyzed stereoconvergent allylation of chiral sp3 -hybridized carbon nucleophiles with a racemic mixture of acyclic secondary allylic phosphates is reported. In the presence of a copper-catalyst complexed with chiral BenzP* ligand, tandem coupling reaction of vinyl arenes, bis(pinacolato)diboron, and racemic allylic phosphates provided β-chiral alkylboronates possessing (E)-alkenyl moiety through a direct stereoconvergent allylic coupling with concomitant generation of a C(sp3 )-stereogenic center. A range of vinyl (hetero)arenes and secondary allylic phosphates bearing 1°, 2°, 3° alkyl and phenyl α-substituents were suitable for the reaction, forming products with high enantioselectivities up to 95 % ee. Density functional theory calculations were conducted in detail to elucidate the origin of the observed regioselectivity of borylcupration and stereoconvergent (E)-olefin formation from racemic allylic phosphates. |
| Databáze: | OpenAIRE |
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