Abnormally high reactivity of the vinyl hydrogen toward singlet oxygen in a twisted 1,3-diene

Tetrahedron Letters

Volumn 37, Issue 43, 1996, Pages 7771-7774

  Mori, Hajime ^a   Ikoma, Keiichi ^a   Masui, Yukio ^b   Isoe, Sachihiko ^b   Kitaura, Kazuo ^b   Katsumura, Shigeo ^a  

^a KWANSEI GAKUIN UNIVERSITY   (Japan)

^b Osaka Prefecture University   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ALKADIENE;

ARTICLE; DRUG STRUCTURE; DRUG SYNTHESIS; MOLECULAR DYNAMICS;

EID: 0030597039     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/0040-4039(96)01774-1     Document Type: Article

References (25)

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2. (b) Holmes, H. L.; The Diels Alder Reaction : Ethylenic and Acetylenic Dienophiles in Organic Reactions; Adams, R. et al. Eds; John wiley & Sons, Inc.: New York 1948, vol 6, pp60 ∼ 73.
3. (c) Ciganek, E.; The Intramolecular Diels-Alder Reaction in Organic Reactions; Dauben, W. G. et al. Eds; John wiley & Sons, Inc.: New York 1984, vol32, pp1∼374.
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8. 3. (a) Ramamurthy, V.; Bopp, T. T.; Liu, R. S. H. Tetrahedron Lett, 1972, 3915.
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10. (c) Honig, B.; Hudson, B.; Sykes, B. D.; Karplus, M. Proc. Nat. Acad. Sci., 1971, 68, 1289.
11. 1=phenyl), respectively.
12. 2 or DMF), while treatment of 1c with a more bulky silyl reagent (TBDMSCl) completely recovered the starting material.
13. 6. In the absence of the phosphine reducing agents, the yields of 3 and 4 were very poor. Oxygenation of these reducing reagents with singlet oxygen would be slower than that of the substrates; Turner, J. A.; Herz, W. J. Org. Chem., 1977, 42, 1657.
14. 3) δ 153.25, 145.67, 135.28, 131.92, 111.67, 108.81, 80.00, 73.22, 39.52, 36.61, 29.33, 24.04, 23.53, 22.90.; HRMS calcd for C15H24O2 236.1770, found 236.1775.
15. 8. Full details of the cristallographic structure analysis of 1 d will be described in the full paper.
16. 9. The geometries were optimized with CFF91 forcefield by use of software packages Insight II 2.1.0 Program. Biosym Technol. Inc. San Diego, U. S. A., and with semiempirical method (PM3) by use of SPARTAN version 3.1, 4.0 Wavefunction, Inc., Irvine, CA.
17. 10. (a) Inagaki, S.; Fukui, K. J. Am. Chem. Soc., 1975, 97, 7480.
18. (b) Inagaki, S.; Fujimoto, H.; Fukui, K. Chem. Lett., 1976, 749.
19. (c) Stephenson, L. M. Tetrahedron Lett., 1980, 21, 1005.
20. 11. The perepoxide intermediate of an ene-reaction with singlet oxygen has been accepted to simple systems, in which abstracted hydrogens have similar reactivity one another : (a) Orfanopoulos, M.; Smonou, I.; Foote, C. S. J. Am. Chem. Soc., 1990, 112, 3607.
21. (b) Orfanopoulos, M.; Stratakis, M.; Elemes, Yiannis. J. Am. Chem. Soc., 1990, 112, 6417.
22. (c) Adam, W.; Richter, M. J. Tetrahedron Lett., 1993, 34, 8423. In the present paper, we focus the interactions of LUMO of singlet oxygen with HOMO of olefins in order to compare the relative reactivity of quite different type hydrogens, that is, C-7 vinyl hydrogen and C-11 allyl hydrogen, toward singlet oxygen.
23. 12. The relative electron densities of frontier orbitals were calculated with HF/3-21G level by use of software packages SPARTAN version 3.1, 4.0 Wavefunction., Inc., Irvine, CA.
24. 13. Full details of the frontier electron densities of 2c-2 and the related compound will be described in the full paper.
25. 14. Further study on the reactivity of significantly twisted 1,3-dienes is under investigation from the view point of σ-π orbital interactions.