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Regiodivergent Synthesis of ortho ‐ and para ‐Cannabinoquinones
Author(s) -
Mattoteia Daiana,
TaglialatelaScafati Orazio,
Muñoz Eduardo,
de la Vega Laureano,
Caprioglio Diego,
Appendino Giovanni
Publication year - 2020
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.202001258
Subject(s) - chemistry , regioselectivity , tautomer , organic chemistry , valence (chemistry) , oxidative phosphorylation , stereochemistry , combinatorial chemistry , catalysis , biochemistry
Spurred by the remarkable biological profile of cannabinoquinoids, we have systematically investigated the periodinane oxidation of their resorcinolic precursors, discovering that the regiochemistry of oxidation, a critical maneuver for bioactivity, depends not only on the nature of the oxidant (λ 3 ‐ vs. λ 5 ‐iodanes), but also on post‐oxidative prototropic‐ and valence tautomeric equilibria that isomerize ortho ‐quinones to para ‐quinones. By complementary selection of the periodinane oxidant and by freezing prototropic equilibration with O ‐methylation, isomeric ortho ‐ and para ‐quinones could be obtained from mono‐ and diphenolic cannabinoids, setting the stage for the exploration of novel areas of the biological space, and establishing a blueprint for the extension of this strategy to other classes of bioactive alkylresorcinols.