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STEREOCHEMISTRY IN LONG-CHAIN BIRADICAL CYCLIZATION

Hasegawa, Tadashi    (Dept. of Chemistry, Saitama University   ); Yamazaki, Yuko    (Department of Chemistry, Tokyo Gakugei University   ); Yoshioka, Michikazu    (Dept. of Chemistry, Saitama University  );
  • 초록

    The structures of 8-membered azalactone isomers produced from photocyclization of 2-(N,N-dibenzylamino)ethyl benzoylacetate were determined by the X-ray structure analysis to clarify the stereochemical behavior of a 1,8-biradical. The remarkable stereoselectivity in cyclization of the 1,8-biradical to form cis- and trans-isomers of the azalactone was not observed. The ring conformations were boat-chair like and dihedral angles between C$_5$- and C$_6$- phenyl groups were ca 45$\circ$ in the both isomers. The 1,8-biradicals in the transition state for the cyclization would have nearly same boat-chair like conformation and twisted configuration with the dihedral angle of ca 45$\circ$ as the corresponding isomer, and this is responsible for luck of stereoselectivity in long-chain biradical cyclization.


  • 참고문헌 (36)

    1. Remote photocyclization of (diben-zylamino)ethyl benzoylacetate. Intermolecular hydrogen abstraction through a ten-membered cyclic transition state , Hasegawa, T.;K. Miyata;T. Ogawa;N. Yoshihara;M. Yoshioka , J. Chem. Soc. Chem. Commun. / v.,pp.363-364,
    2. Direct methods for difference structures-An automatic procedure for phase extension and refinement of difference estructrue factors , Beurskens, P. T. , Technical Report 1984 / v.,pp.,
    3. Photochemical reactions of 4-oxo carboxylic esters : Remote hydrogen abstraction and eistrans isomerization , Hasegawa, T.;K. Takashima;H. Aoyama;M. Yoshioka , Bull. Chem. Soc. Jpn. / v.65,pp.3498-3500,
    4. Photosensitizations by reversible electron transfer : Theories, experimental evidence and examples , Kavarnos, G. J.;N. J. Turro , Chem. Rev. / v.86,pp.401-449,
    5. Type II photoprocesses of pheny1 ketones. Competitive δ-hydrogen abstration and the geometry of intramolecular hydrogen atom transfers , Wagner, P. J.;P. A. Kelso;A. E. Kemppaonen;R. G. Zepp , J. Am. Chem. Soc. / v.94,pp.7500-7506,
    6. Dispersion corrections and crystal structure refinements , Ibers, J. A.;W. C. Hamilton , Acta Crystallogr. / v.17,pp.781,
    7. Photoclization of α-[0-(benzyloxy)pheny1]acetophenone : Triplet-state ε-hydrogen abstraction , Meador, M. A.;P. J. Wagner , J. Org. Chem. / v.50,pp.419-420,
    8. Molecular geometry. V. Evaluation of functions and conformations of medium rings , Hendrickson, J. B. , J. Am. Chem. Soc. / v.89,pp.7036-7043,
    9. Photochemical probes of hydrocarbon chain conformation in solustion , Winnik, M. A. , Acc. Chem. Res. / v.10,pp.173-179,
    10. Conformational analysis of hydrocarbon chains in solution. Carbon tetracholride , Winnik, M. A.;C. K. Lee;S. Basu;D. S. Saunder , J. Am. Chem. Soc. / v.96,pp.6182-6184,
    11. 1.5-and 1.9-hydrogen atom abstractions. Photochemical strategies for radical cyclization , Kraus, G. A.;Y. Wu , J. Am. Chem. Soc. / v.114,pp.8705-8707,
    12. Type II photoelimination and photocyclization of ketones , Wagner, P.J. , Acc. Chem. Res. / v.4,pp.168-177,
    13. Photorearrangements via biradicals of simple carbonyl compounds , Wagner, P. J.;Mayo P.(ed.) , Rearrangements in Ground and Excited States / v.Essay 20,pp.381-444,
    14. Conformational flexibility and photochemistry , Wagner, P.J. , Acc. Chem. Res. / v.16,pp.461-467,
    15. Synthesis and photochemistry of some new pentacy-cloundecan-8-ones. Probes for hydrogen adstraction in the π-plane , Sauers, R. R.;A. Scimone;H. Shams , J. Org. Chem. / v.53,pp.6084-6089,
    16. Photochemical ε-hydrogen abstraction as a route to tetrahydropyran-3-ols , Carless, H. A. J.;G. K. Fekarurhobo , Tetrahedron Lett. / v.25,pp.5943-5946,
    17. Biomimetic control of chemical selectivity , Breslow, R. , Acc. Chem. Res. / v.13,pp.170-177,
    18. Cyclic aminoacyloins and aminoketones. V. Detailed infarared spectral study of transnnular interaction between N and $C_{CO}$ , Leonard, N. J.;M. Oki;J. Brader;H. Boaz , J. Am. Chem. Soc. / v.77,pp.6237-6239,
    19. Intramolecular hydrogen abstraction in ketone photochemistry : The first examples of ζ-hydrogen abstraction , Carless, H. A. J.;S. M.-Kibenda , J. Chem. Soc. Chem. Commun. / v.,pp.1673-1674,
    20. Kluwer Academic Publishers , International Tables for X-ray Crystallography / v.IV,pp.149,
    21. Photoinduced hydrogen atom abstraction by carbonyl compounds , Wagner, P. J.;B. -S. Park;Padwa, A.(ed.) , Organic Photochemistry / v.11,pp.227-366,
    22. Kluwer Academic Puplishers , International Tables for X-ray Crystallography / v.IV,pp.72-73,
    23. Cyclization and the conformation of hydrocarbon chains , Winnik, M. A. , Chem. Rev. / v.81,pp.491-524,
    24. Molecular Strucature Corporation , TEXSAN-TEXRAY Structure Analysis Package / v.,pp.,
    25. Photoeyelization of co-(dialkylamino)alkyl β-oxoesters via remote hydrogen transfer , Hasegawa,T.;T. Ogawa;K. Miyata;A. Karakizawa;M. Komiyama;K. Nishizawa;M. Yoshioka , J. Chem. Soc. Perkin Trans. / v.1,pp.901-905,
    26. Photocyclization of 2-(dialiylamino)ethyl acetoactates : Remote proton transfer and Stern-Volmer quenching kineties in the system involving two reactive excited states , Haesgawa, T.;N. Tasuda;M. Yoshioka , J. Phys. Org. Chem. / v.9,pp.221-226,
    27. Cyclic aminoacyloins and aminoketones, IV. Dependence of transnnular interaction upon the relative location of N and $C_{CO}$ , Leonard, N. J.;M. Oki;S. Chiavarelli , J. Am. Chem. Soc. / v.77,pp.6224-6237,
    28. 1,5-Biradicals and five-membered rings generates by δ-hydrogen abstraction in photoexcited ketones , Wagner, P. J. , Acc. Chem. Res. / v.22,pp.83-91,
    29. Photochemistry of methyl-substituted butyrophenones. The nature of the 1,4-biradical interrnediates , Lewis, F. D.;T. A. Hilliard , J. Am. Chem. Soc. / v.92,pp.6672-6674,
    30. Photoreactions of 2-(dialkyamino)ethyl esters of γ-oxo acids via remote hydrogen transfer : Influence of the stability and confromational flexibility of the biradical intermediate on its chemical behavior , Hasegawa, T.;K. Mukai;K. Mizukoshi;M. Yoshioka , Bull. Chem. Soc. Jpn. / v.63,pp.3348-3350,
    31. Novel biradical cyclization via remotehydrogen transfer in photochemistry of 2-dialkyl-aminoethyl 3-benzoyacrylates , Hasegawa, T.;Y. Yamazaki;M. Yochioka , Bull. Chem. Soc. Jpn. / v.66,pp.3128-3131,
    32. Photoreduction by amines , Cohen, S. G.;A. Parola;G. H. Parsons. Jr. , Chem. Rev. / v.73,pp.141-161,
    33. A simple method to perform a liquid diffusion crystallization , Orvig, C. , J. Chem. Ed. / v.62,pp.84,
    34. Stereoelectronic requirements for the type II cleavage of cis-and trans-4-t-butylcyclohexanones , Turro, N. J.;D. S. Weiss , J. Am. Chem. Soc. / v.90,pp.2185-2186,
    35. Photocyclization of β-oxesters : Limiting factors for remote hydrogen abstraction through a medium-sized cyclic transition state , Hasegawa, T.;Y. Horikoshi;S. Iwata;M. Yahioka , J. Chem. Soc. Chem. Commun. / v.,pp.1617-1618,
    36. MITHRIL-An integrated direct methods computer program , Gilmore, C. J. , J. Appl. Cryst. / v.17,pp.42-46,
  • 이 논문을 인용한 문헌 (1)

    1. 1997. "" Journal of photoscience : an international journal officail organ of the korean society of photoscience, 4(2): 61~67     

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