Enantioselective Inverse-Electron Demand Aza-Diels–Alder Reaction: ipso,α-Selectivity of Silyl Dienol Ethers
| Autor: | Jorge Humbrías-Martín, José Alemán, Víctor Laina-Martín, José A. Fernández-Salas, Rubén Mas-Ballesté |
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| Přispěvatelé: | UAM. Departamento de Química Inorgánica, UAM. Departamento de Química Orgánica |
| Rok vydání: | 2021 |
| Předmět: |
Bifunctional catalysis
Silylation Ether 010402 general chemistry 01 natural sciences Catalysis Diels−Alder chemistry.chemical_compound Nucleophile Benzofuran derivatives Aza-Diels–Alder reaction Organocatalysis 010405 organic chemistry Hydrogen-bonding activation Squaramide Enantioselective synthesis Química General Chemistry Enol Combinatorial chemistry 0104 chemical sciences chemistry Hemiaminal Research Article |
| Zdroj: | ACS Catalysis Biblos-e Archivo. Repositorio Institucional de la UAM instname |
| ISSN: | 2155-5435 2018-0950 |
| Popis: | A highly efficient enantioselective inverse-electron-demand aza-Diels-Alder reaction between aza-sulfonyl-1-aza-1,3-butadienes and silyl (di)enol ethers has been developed. The presented methodology allows the synthesis of benzofuran-fused 2-piperidinol derivatives with three contiguous stereocenters in a highly selective manner, as even the hemiaminal center is completely stereocontrolled. Density functional theory (DFT) calculations support that the hydrogen-bond donor-based bifunctional organocatalyst selectively triggers the reaction through the ipso,α-position of the dienophile, in contrast to the reactivity observed for dienolates in situ generated from β,γ-unsaturated derivatives. Moreover, the calculations have clarified the mechanism of the reaction and the ability of the hydrogen-bond donor core to hydrolyze selectively theEisomer of the dienol ether. Furthermore, to demonstrate the applicability of silyl enol ethers as nucleophiles in the asymmetric synthesis of interesting benzofuran-fused derivatives, the catalytic system has also been implemented for the highly efficient installation of an aromatic ring in the piperidine adducts Financial support was provided by the European Research Council (ERC-CoG, contract number: 647550), Spanish Government (RTI2018-095038-B-I00), and “Comunidad de Madrid” and European Structural Funds (S2018/NMT-4367) |
| Databáze: | OpenAIRE |
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