title: [1,4]-sigmatropic rearrangement of chiral nitrones and their utilization in the synthesis of new iminosugars.
abstract: Reflection on the epimerization of the α-stereocenter of sugar nitrones leads to the conclusion that the process may occur through [1,4]-sigmatropic rearrangement. Participation of an ionic mechanism was excluded by a deuterium labeling experiment, and DFT calculations showed a reasonable energy barrier for the proposed [1,4]-shift. Products of the intramolecular 1,3-dipolar cycloaddition of the studied nitrones were utilized in the diversity-oriented synthesis of polyhydroxy derivatives of piperidine, indolizidine and quinolizidine. Minimal activity against the screened glucosidases and human melanoma cell lines was observed for some of the obtained compounds.
authors.affiliation: Faculty of Chemistry, Warsaw University of Technology, ul. Noakowskiego 3, 00-664 Warsaw, Poland. tomek@ch.pw.edu.pl.
authors.forename: Maciej
authors.initials: M
authors.lastname: Malinowski
authors.forename: Tomasz
authors.initials: T
authors.lastname: Rowicki
authors.forename: Patrycja
authors.initials: P
authors.lastname: Guzik
authors.forename: Maciej
authors.initials: M
authors.lastname: Gryszel
authors.forename: Sebastian
authors.initials: S
authors.lastname: Łapczyński
authors.forename: Monika
authors.initials: M
authors.lastname: Wielechowska
authors.forename: Karolina
authors.initials: K
authors.lastname: Czerwińska
authors.forename: Izabela
authors.initials: I
authors.lastname: Madura
authors.forename: Wojciech
authors.initials: W
authors.lastname: Sas
mesh_terms: D045744:Cell Line, Tumor; D049109:Cell Proliferation / Q000187:drug effects; D002470:Cell Survival / Q000187:drug effects; D004305:Dose-Response Relationship, Drug; D004791:Enzyme Inhibitors / Q000138:chemical synthesis / Q000737:chemistry / Q000494:pharmacology*; D005959:Glucosidases / Q000037:antagonists & inhibitors* / Q000378:metabolism; D006801:Humans; D050111:Imino Sugars / Q000138:chemical synthesis* / Q000737:chemistry / Q000494:pharmacology*; D008958:Models, Molecular; D015394:Molecular Structure; D009589:Nitrogen Oxides / Q000737:chemistry*; D011789:Quantum Theory; D013237:Stereoisomerism; D013329:Structure-Activity Relationship; D013816:Thermodynamics
chemical_list: D004791:Enzyme Inhibitors; D050111:Imino Sugars; D009589:Nitrogen Oxides; C015388:nitrones; D005959:Glucosidases