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  • Diels-Alder reactions  (2)
  • Inorganic Chemistry  (1)
  • 1
    ISSN: 0009-2940
    Keywords: ortho-Quinones ; tert-Butyl hydroperoxide ; Phenols, oxygenation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Eine neue ortho-Chinon-Synthese durch Oxygenierung von Phenolen mit den Systemen tert-Butylhydroperoxid/Übergangsmetall-Komplex und dem Mimounschen Oxodiperoxo-Molydbän-Komplex [Mo(O2)2O] · py · HMPTPhenole können mit einer Kombination der Übergangsmetall-Komplexe Ti(OiPr)4, VO(acac)2, Zr(acac)4, Zr(OnPr)4 und tert-Butylhydroperoxid oder mit [Mo(O2)2O] · Py · HMPT spezifisch zu ortho-Chinonen oxygeniert werden. Naphthole, Anthracenole, Phenanthrole und Donor-substituierte einkernige Phenole werden glatt in die entsprechenden 1,2-Chinone übergeführt. Ungehinderte ortho-Napthochinone können unter Michael-Addition mit nicht umgesetztem Ausgangsmaterial zu Biarylen abreagieren.
    Notes: A specific oxygenation of phenols to ortho-quinones can be effected by a combination of the transition metal complexes Ti(OiPr)4, VO(acac)2, Zr(acac)4, Zr(OnPr)4 and tert-butylhydroperoxide (TBHP) or [Mo(O2)2O] · Py · HMPT. Naphthols, anthracenols, phenanthrols and donor substituted mononuclear phenols are readily converted into the corresponding 1,2-quinones. Unhindered ortho-naphthoquinones can yield binaphthyls with unreacted starting material by Michael addition.
    Additional Material: 1 Tab.
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  • 2
    ISSN: 0947-3440
    Keywords: Angucyclinones ; MM 47755 ; X-14881 E ; Diels-Alder reactions ; Silicon-oxygen exchange ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Diels-Alder reactions of the naphthoquinones 1-4 with the dienes 5a-7 were investigated. The regioisomeric outcome of the adducts 10a-10g, 16, and 23 is in agreement with theoretical predictions from frontier orbital calculations. The adduct 10a was further converted to the non-natural (e.g. 15) and the adduct 16 to the natural angucyclinones MM 47755 (19a) and X-14881 E (22) by silicon-oxygen exchange and photooxygenation. The addition of naphtoquinones 2 and 4 to dienes 6 and 7 afford the Diels-Alder adducts 16 and 23, respectively, which are valuable intermediates for further transformation into non-aromatic angucyclinones.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1995 (1995), S. 1981-1985 
    ISSN: 0947-3440
    Keywords: Angucyclines ; Diels-Alder reactions ; Photooxygenation ; Methoxylation ; Osmylation ; X-ray ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Osmylation of the Diels-Alder adduct 3 afforded the cis-diol 4, which was dehydrated by acid treatment to the phenol 6. Reaction with tetrafluoroboric acid converted the diol 4 by intramolecular acyl shift into the acetate 7. The relative stereochemistry of 7 was determined by single-crystal X-ray analysis. Photooxygenation of 4 afforded the C-1 carbonyl compound 8 and treatment with sulfuric acid the silanol 9. Functionalization of C-6 was achieved by treatment of 4 with methanolic KOH to yield the cis-methyl ether 11.
    Additional Material: 1 Ill.
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