Trost, B. M.; Osipov, M.; Krueger, S.; Zhang, Y.: A catalytic asymmetric total synthesis of (-)-perophoramidine. In: Chemical Science 6 (2015), Nr. 1, S. 349-353. DOI:
http://dx.doi.org/10.1039/c4sc01826e
Zusammenfassung: |
We report a catalytic asymmetric total synthesis of the ascidian natural product perophoramidine. The synthesis employs a molybdenum-catalyzed asymmetric allylic alkylation of an oxindole nucleophile and a monosubstituted allylic electrophile as a key asymmetric step. The enantioenriched oxindole product from this transformation contains vicinal quaternary and tertiary stereocenters, and is obtained in high yield along with high levels of regio-, diastereo-, and enantioselectivity. To install the second quaternary stereocenter in the target, the route utilizes a novel regio- and diastereoselective allylation of a cyclic imino ether to deliver an allylated imino ether product in near quantitative yield and with complete regio- and diastereocontrol. Oxidative cleavage and reductive amination are used as final steps to access the natural product.
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Lizenzbestimmungen: |
CC BY-NC 3.0 Unported - http://creativecommons.org/licenses/by-nc/3.0/
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Publikationstyp: |
Article |
Publikationsstatus: |
publishedVersion |
Erstveröffentlichung: |
2014-07-30 |
Schlagwörter (deutsch): |
enantioselektive allylische Alkylierung, Bindungsbildung, Synthese, (+)-Perophoramidin, Perophoramidin, Perophora namei, Indol, Pd, Palladium
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Schlagwörter (englisch): |
enantioselective allylic alkylation, bond formation, (+)-perophoramidine, indoles, Pd, palladium, Perophora namei
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Fachliche Zuordnung (DDC): |
540 | Chemie
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Kontrollierte Schlagwörter: |
Alkylierung, Chemische Bindung, Alkaloide, Seescheiden, Indol, Palladium
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