Novel Baeyer–Villiger-type oxidation of 4,5-epoxymorphinan derivatives

[Display omitted] •A novel molecular oxygen-mediated Baeyer–Villiger-type oxidation has been discovered.•The reaction proceeds specifically to the morphinan skeleton.•The products would be useful for designing highly selective and potent KOR agonists. A novel molecular oxygen-mediated Baeyer–Villige...

Full description

Saved in:
Bibliographic Details
Published inTetrahedron letters Vol. 63; pp. 152714 - 152717
Main Authors Hino, Tsubasa, Kutsumura, Noriki, Saitoh, Tsuyoshi, Yamamoto, Naoshi, Nagumo, Yasuyuki, Mogi, Yuzo, Watanabe, Yoshikazu, Nagase, Hiroshi
Format Journal Article
LanguageEnglish
Published OXFORD Elsevier Ltd 19.01.2021
Elsevier
Subjects
Chemistry
Chemistry, Organic
Molecular oxygen
Morphinan
Physical Sciences
Reaction mechanism
Rearrangement
Science & Technology
κ Opioid receptor agonist
Reaction mechanism
Molecular oxygen
Morphinan
κ Opioid receptor agonist
Rearrangement
DESIGN
RECEPTOR
kappa Opioid receptor agonist
REARRANGEMENTS
OPIOID LIGANDS
AGONIST
Online AccessGet full text

Cover

More Information
Summary:[Display omitted] •A novel molecular oxygen-mediated Baeyer–Villiger-type oxidation has been discovered.•The reaction proceeds specifically to the morphinan skeleton.•The products would be useful for designing highly selective and potent KOR agonists. A novel molecular oxygen-mediated Baeyer–Villiger-type oxidation specific to the morphinan skeleton has been discovered. The reaction of a ketone bearing a bicyclo[2.2.2]octenone skeleton with KOH (pellet) in refluxing tBuOH under an oxygen atmosphere (balloon) afforded unexpected cyclopropanecarboxylic acid and ketolactone derivatives. The reactive sites (carboxylic acid and ester) in those products are oriented over the C-ring in the morphinan skeleton, and thus such morphinan compounds would be useful intermediates to design ideal κ opioid receptor agonists.
ISSN:0040-4039
1873-3581
DOI:10.1016/j.tetlet.2020.152714