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Volumn , Issue 26, 2007, Pages 4305-4312

Synthesis of a norsesquiterpene spirolactone/steroidal hybrid by using an environmentally friendly domino reaction as a key step

Author keywords

Domino reactions; Hybrid molecules; Iodobenzene diacetate; Lead tetraacetate; Natural products

Indexed keywords


EID: 34548736048     PISSN: 1434193X     EISSN: 10990690     Source Type: Journal    
DOI: 10.1002/ejoc.200700446     Document Type: Article
Times cited : (23)

References (44)
  • 6
    • 0030751681 scopus 로고    scopus 로고
    • 2: F. De Riccardis, I. Izzo, M. Di Filippo, G. Sodano, F. D'Acquisto, R. Carnuccio, Tetrahedron 1997, 53, 10871-10882.
    • 2: F. De Riccardis, I. Izzo, M. Di Filippo, G. Sodano, F. D'Acquisto, R. Carnuccio, Tetrahedron 1997, 53, 10871-10882.
  • 8
    • 0022971248 scopus 로고    scopus 로고
    • Proscar, developed by Merck Sharp & Dohme (a) G. H. Rasmusson, G. F. Reynolds, N. G. Steinberg, E. Walton, G. F. Patel, T. Liang, M. A. Cascieri, A. H. Cheung, J. R. Brooks, C. Berman, J. Med. Chem. 1986, 29, 2298-2315), and episteride, developed by SmithKline Beecham
    • Proscar, developed by Merck Sharp & Dohme (a) G. H. Rasmusson, G. F. Reynolds, N. G. Steinberg, E. Walton, G. F. Patel, T. Liang, M. A. Cascieri, A. H. Cheung, J. R. Brooks, C. Berman, J. Med. Chem. 1986, 29, 2298-2315), and episteride, developed by SmithKline Beecham
  • 9
    • 0028083310 scopus 로고    scopus 로고
    • P. R. Audet, N. H. Baine, L. J. Benincosa, D. A. Holt, P. J. Wier, E. B. Rappaport, B. W. Metcalf, M. Levy, Drugs Future 1994, 19, 646-650, are both modified steroids with changes localized on the A ring and on segments attached at the C17 position of the steroid nucleus.
    • (b) P. R. Audet, N. H. Baine, L. J. Benincosa, D. A. Holt, P. J. Wier, E. B. Rappaport, B. W. Metcalf, M. Levy, Drugs Future 1994, 19, 646-650), are both modified steroids with changes localized on the A ring and on segments attached at the C17 position of the steroid nucleus.
  • 12
  • 14
    • 0001847186 scopus 로고    scopus 로고
    • Eds, M. Shibasaki, J. F. Stoddart, F. Vögtle, Wiley-VCH, Weinheim
    • d) L. F. Tietze, F. Haunert, in Stimulating Concepts in Chemistry (Eds.: M. Shibasaki, J. F. Stoddart, F. Vögtle), Wiley-VCH, Weinheim, 2000, p. 39-64;
    • (2000) Stimulating Concepts in Chemistry , pp. 39-64
    • Tietze, L.F.1    Haunert, F.2
  • 15
    • 84890766709 scopus 로고    scopus 로고
    • Eds, L. F. Tietze, G. Brasche, K. M. Gericke, Wiley-VCH
    • e) Domino Reactions in Organic Synthesis (Eds.: L. F. Tietze, G. Brasche, K. M. Gericke), Wiley-VCH, 2006.
    • (2006) Domino Reactions in Organic Synthesis
  • 26
    • 34548758532 scopus 로고    scopus 로고
    • It should be pointed out that the absolute stereochemistry of pathylactone A was assigned by the CD method, while a racemic synthesis of 1a, and allegedly of 1-epipathylactone A, has raised doubts about the spectral assignments of the norsesquiterpene natural product
    • It should be pointed out that the absolute stereochemistry of pathylactone A was assigned by the CD method, while a racemic synthesis of 1a, and allegedly of 1-epipathylactone A, has raised doubts about the spectral assignments of the norsesquiterpene natural product.
  • 31
    • 34548771241 scopus 로고    scopus 로고
    • Since the overall process resulting in the introduction of new stereogenic centres proceeds through a rehybridisation of the two sp3 centres, the C2 and C3 stereochemistry of the starting diols is not of concern, and hence, no chromatographic separation at this level is needed
    • 3 centres, the C2 and C3 stereochemistry of the starting diols is not of concern, and hence, no chromatographic separation at this level is needed.
  • 32
    • 34548747522 scopus 로고    scopus 로고
    • We use norsesquiterpene spirolactone numbering for the left half (A′, B′ rings) while a marked steroid numbering (i.e. 17′) is applied for the right half (C, D rings) throughout the text, starting at 6
    • We use norsesquiterpene spirolactone numbering for the left half (A′, B′ rings) while a marked steroid numbering (i.e. 17′) is applied for the right half (C, D rings) throughout the text, starting at 6.
  • 33
    • 14344253493 scopus 로고    scopus 로고
    • This one-step conversion of unsaturated diols to cyclic ene-acetals is operative in a wide range of solvents; Ö. Sesenoglu, J. I. Candela Lena, E. Altinel, N. Birlirakis, S. Arseniyadis, Tetrahedron: Asymmetry 2005, 16, 995-1015
    • This one-step conversion of unsaturated diols to cyclic ene-acetals is operative in a wide range of solvents; Ö. Sesenoglu, J. I. Candela Lena, E. Altinel, N. Birlirakis, S. Arseniyadis, Tetrahedron: Asymmetry 2005, 16, 995-1015.
  • 35
    • 85033148217 scopus 로고    scopus 로고
    • 2+ but without the toxic and environmental issues: a R. M. Moriarty, R. K. Vaid, Synthesis 1990, 431-447;
    • 2+ but without the toxic and environmental issues: a) R. M. Moriarty, R. K. Vaid, Synthesis 1990, 431-447;
  • 37
    • 34548775149 scopus 로고    scopus 로고
    • Ratios of the ozonolysis products were determined by comparing the integrated areas for the aldehyde proton signal of formyl aldehyde 7 at δ, 8.00 ppm, the C9 aldehyde proton signal of 8 at δ, 10.00 ppm, the C11 proton doublet at δ, 5.60 ppm and the C9 proton singlet adjacent to the C6 quaternary centre at δ, 4.95 ppm of 9a. Insofar as a mechanistic rationale is concerned, it is conceivable that the initial product, zwitterion ii, formed by the cycloreversion of the primary ozonide i, may in part be trapped by methanol to give α-hydroperoxide methyl ether iv which then undergoes reduction to afford the corresponding hemiacetal v and a subsequent transacetalisation ending in 9a Scheme 2, Given the fact that the carbonyl and zwitterion moieties are situated in the same molecule, secondary ozonide formation remains a competitive path. Two test reactions were performed, attempting to prove that i
    • 1H NMR (diagnostic region) of the crude mixture is included in the Supporting Information. (Chemical Equation Presented)
  • 38
    • 34548717662 scopus 로고    scopus 로고
    • It should be pointed out that some spontaneous spirolactonisation happened also on standing in solution or during the SiO2 column chromatography
    • 2 column chromatography.
  • 41
    • 34548723935 scopus 로고    scopus 로고
    • In our hands, the Wacker oxidation did not produce synthetically useful results proceeding in modest yields ca. 50, Furthermore, an accompanying byproduct, inseparable by column chromatography, was present, rendering the two-step elaboration of the methyl ketone moiety unproductive
    • In our hands, the Wacker oxidation did not produce synthetically useful results proceeding in modest yields (ca. 50%). Furthermore, an accompanying byproduct, inseparable by column chromatography, was present, rendering the two-step elaboration of the methyl ketone moiety unproductive.
  • 42
    • 34548810319 scopus 로고    scopus 로고
    • Coelho et al. observed a similar behaviour upon fluoride-induced desylilation in ref.[9b
    • [9b]


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.