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Volumn 346, Issue 11, 2004, Pages 1367-1374

Carbene rearrangements, 60. Supramolecular structure-reactivity relationships: Photolysis of a series of aziadamantane@cyclodextrin inclusion complexes in the solid state

Author keywords

Carbenes; Cyclodextrins; Diazirines; Photolysis; Supramolecular chemistry

Indexed keywords

CARBENE; CYCLODEXTRIN;

EID: 7044260731     PISSN: 16154150     EISSN: None     Source Type: Journal    
DOI: 10.1002/adsc.200404142     Document Type: Article
Times cited : (20)

References (58)
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    • ‡ For Part 59, see: T. Nordvik, J.-L. Mieusset, U. H. Brinker, Org. Lett. 2004, 6, 715-718; Carbenes in Constrained Systems. 9. For part 8, see: M. G. Rosenberg, U. H. Brinker, J. Org. Chem. 2003, 68, 4819-4832.
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    • Nordvik, T.1    Mieusset, J.-L.2    Brinker, U.H.3
  • 2
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    • ‡ For Part 59, see: T. Nordvik, J.-L. Mieusset, U. H. Brinker, Org. Lett. 2004, 6, 715-718; Carbenes in Constrained Systems. 9. For part 8, see: M. G. Rosenberg, U. H. Brinker, J. Org. Chem. 2003, 68, 4819-4832.
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    • ‡ For Part 59, see: T. Nordvik, J.-L. Mieusset, U. H. Brinker, Org. Lett. 2004, 6, 715-718; Carbenes in Constrained Systems. 9. For part 8, see: M. G. Rosenberg, U. H. Brinker, J. Org. Chem. 2003, 68, 4819-4832.
    • (2003) J. Org. Chem. , vol.68 , pp. 4819-4832
    • Rosenberg, M.G.1    Brinker, U.H.2
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    • note
    • Primary products resulting from C-H insertion of Ad: into the inner C-H bonds (3′ and 5′ of the glucose moieties) of α-cyclodextrin thus far have never been identified, although the contact with these protons is expected to be quite close. Embedded within the crystal of the 1@2(6-Cy) complex, such a product might be quite strained. Thus the primarily formed tertiary alcohol at C-3′ could be oxidized by a Cannizzaro-like reaction to a ketone with concomitant extrusion of the reduced hydrocarbon 2. Admittedly, this is a more speculative explanation for the high yield of adamantane (2) observed only in this particular case.
  • 46
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    • note
    • Thermal decomposition of the 1@2(6-Cy) complex at 230°C or 300°C also yields 2 as the major volatile compound. In these pyrolytic reactions a considerable amount of material decomposed so that quantitative yields are of little significance. An absolute yield of 12% was determined for 2 with a total recovery of adamantanyl residues of only 25% (by analysis of the compounds also found in photolytic experiments).
  • 47
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    • note
    • Minute amounts of a third cyclodextrin derivative can be traced, but only in experiments at low temperature.
  • 50
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    • a) M. S. Platz, in: Advances in Carbene Chemistry, Vol. 2, (Ed.: U. H. Brinker), JAI, Stamford, CT, 1998, pp. 133-174;
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    • (Ed.: U. H. Brinker), Elsevier, Amsterdam
    • c) D. C. Merrer, R. A. Moss, in: Advances in Carbene Chemistry, Vol. 3, (Ed.: U. H. Brinker), Elsevier, Amsterdam, 2001, pp. 53-113.
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    • Merrer, D.C.1    Moss, R.A.2


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.