Cascade polyene cyclization reactions are highly efficient and elegant bioinspired transformations that involve simultaneous multiple bond constructions to rapidly generate complex polycyclic molecules. This review summarizes the most prominent work on a variety of cationic and radical cascade cyclizations and their applications in natural product synthesis published between 2014 and 2018.1 Introduction2 Cationic Polyene Cyclizations2.1 Lewis Acid Mediated Polyene Cyclizations2.2 Brønsted Acid Mediated Polyene Cyclizations2.3 Halogen Electrophile Initiated Polyene Cyclizations2.4 Sulfur Electrophile Initiated Polyene Cyclizations2.5 Transition-Metal-Mediated Cationic Polyene Cyclizations3 Radical Polyene Cyclizations3.1 Transition-Metal-Mediated Radical Polyene Cyclizations3.2 Photocatalyst-Mediated Polyene Cyclizations4 Origin of Stereocontrol in Polyene Cyclizations5 Conclusion
Biomimetic total syntheses of resorcinols amorphastilbol, grifolin and grifolic acid have been completed in four steps starting from geraniol and farnesol without the use of phenolic protection. The key steps involve C-acylation of dioxinone-β-keto esters, followed by palladium catalyzed decarboxylative allylic rearrangement and biomimetic aromatization.
(+)-Hongoquercin A and B were synthesized
from commercially available trans,trans-farnesol in six and eleven
steps, respectively, using dual biomimetic strategies with polyketide
aromatization and subsequent polyene functionalization from a common
farnesyl-resorcylate intermediate. Key steps involve Pd(0)-catalyzed
decarboxylative allylic rearrangement of a dioxinone β,δ-diketo
ester to a β,δ-diketo dioxinone, which was readily aromatized
into the corresponding resorcylate, and subsequent polyene cyclization
via enantioselective protonation or regioselective terminal alkene
oxidation and cationic cyclization of enantiomerically enriched epoxide
to furnish the tetracyclic natural product cores. Analogues of the
hongoquercin were synthesized via halonium-induced polyene cyclizations,
and the meroterpenoid could be further functionalized via saponification,
hydrolytic decarboxylation, reduction, and amidation reactions.
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