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Download fileTotal Synthesis of Longeracinphyllin A
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posted on 2017-09-28, 00:00 authored by Jian Li, Wenhao Zhang, Fei Zhang, Yu Chen, Ang LiThe first and asymmetric total synthesis
of longeracinphyllin A,
a hexacyclic Daphniphyllum alkaloid, has been accomplished.
A tetracyclic intermediate was prepared through silver-catalyzed alkyne
cyclization and Luche radical cyclization. A phosphine-promoted [3
+ 2] cycloaddition reaction was exploited to construct the sterically
congested E ring bearing vicinal tertiary and quaternary centers.
The cyclopentenone motif was assembled by using intramolecular Horner–Wadsworth–Emmons
olefination. Raney Ni reduction delivered the tertiary amine from
a thioamide precursor at a late stage.
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quaternary centersstericallyE ringLongeracinphyllinintramoleculartetracyclicsilver-catalyzed alkyne cyclizationlongeracinphyllincycloadditionsynthesishexacyclic Daphniphyllum alkaloidolefinationthioamide precursorphosphine-promotedcyclopentenone motifHornerLucheTotal SynthesisRaney Ni reductionvicinalamine