TY - JOUR

T1 - Synthetic transformations of sesquiterpene lactones. Controllable synthesis of 11,13-dihydroisoalantolactone azides and 13-(1,2,3-triazolyl)eudesmanolides based on sesquiterpene lactones

AU - Patrushev, Sergey S.

AU - Rybalova, Tatyana V.

AU - Shults, Elvira E.

N1 - Funding Information: This work was financially supported by a grant from the Russian Science Foundation (project No. 18-13-00361-P). Publisher Copyright: © 2021, Springer Science+Business Media, LLC, part of Springer Nature.

PY - 2021/11

Y1 - 2021/11

N2 - Modification of eudesmane-type lactones isoalantolactone and 4,15-epoxyisoalantolactone was carried out at the active methylene group. The reaction of isoalantolactone with hydrazoic acid, which was formed in situ from sodium azide and acetic acid in the presence of triethylamine in toluene or DMF, proceeds in a controllable manner and, depending on the nature of the solvent and reaction conditions, leads to (11R)-13-azido-11,13-dihydroisoalantolactone, the spirocyclic compound (11R)-aziridino[11,13]dihydroisoalantolactone, and the product of the selective opening of the aziridine ring with the azide anion (11S)-11-amino-13-azido-11,13-dihydroisoalantolactone. The reaction of 4,15-epoxyisoalantolactone with hydrazoic acid proceeds similarly to form the corresponding 13-azido-, (11R)-aziridino[11,13]-, or (11S)-11-amino-13-azido-4,15-epoxy-11,13-dihydroisoalantolactones. The regioselective synthesis of libraries of (11R)-13-(1H-1,2,3-triazolyl)-11,13-dihydroisoalantolactones and (11S)-11-amino-13-(1H-1,2,3-triazolyl)-11,13-dihydroisoalantolactones containing various aryl or hetaryl substituents at the C-4 position of the triazole ring was carried out by the CuAAC reaction of 13-azido-substituted 11,13-dihydroisoalantolactones with terminal acetylenes.

AB - Modification of eudesmane-type lactones isoalantolactone and 4,15-epoxyisoalantolactone was carried out at the active methylene group. The reaction of isoalantolactone with hydrazoic acid, which was formed in situ from sodium azide and acetic acid in the presence of triethylamine in toluene or DMF, proceeds in a controllable manner and, depending on the nature of the solvent and reaction conditions, leads to (11R)-13-azido-11,13-dihydroisoalantolactone, the spirocyclic compound (11R)-aziridino[11,13]dihydroisoalantolactone, and the product of the selective opening of the aziridine ring with the azide anion (11S)-11-amino-13-azido-11,13-dihydroisoalantolactone. The reaction of 4,15-epoxyisoalantolactone with hydrazoic acid proceeds similarly to form the corresponding 13-azido-, (11R)-aziridino[11,13]-, or (11S)-11-amino-13-azido-4,15-epoxy-11,13-dihydroisoalantolactones. The regioselective synthesis of libraries of (11R)-13-(1H-1,2,3-triazolyl)-11,13-dihydroisoalantolactones and (11S)-11-amino-13-(1H-1,2,3-triazolyl)-11,13-dihydroisoalantolactones containing various aryl or hetaryl substituents at the C-4 position of the triazole ring was carried out by the CuAAC reaction of 13-azido-substituted 11,13-dihydroisoalantolactones with terminal acetylenes.

KW - azide-alkyne cycloaddition reaction

KW - click chemistry

KW - sesquiterpene lactones

KW - terpenoid azides

KW - triazoles

KW - X-ray structural analysis

UR - http://www.scopus.com/inward/record.url?scp=85122391336&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/3f38b35c-bc47-3bb5-a321-8f1012b35bea/

U2 - 10.1007/s10593-021-03030-1

DO - 10.1007/s10593-021-03030-1

M3 - Article

AN - SCOPUS:85122391336

VL - 57

SP - 1116

EP - 1129

JO - Chemistry of Heterocyclic Compounds

JF - Chemistry of Heterocyclic Compounds

SN - 0009-3122

IS - 11

ER -