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Volumn 71, Issue 14, 2006, Pages 5328-5339

On the [2+2] cycloaddition of 2-aminothiazoles and dimethyl acetylenedicarboxylate. Experimental and computational evidence of a thermal disrotatory ring opening of fused cyclobutenes

Author keywords

[No Author keywords available]

Indexed keywords

ASSAYS; DERIVATIVES; ELECTRONS; EXTRUSION; ISOMERS; NUMERICAL METHODS; REACTION KINETICS;

EID: 84961974888     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo060664c     Document Type: Article
Times cited : (47)

References (89)
  • 1
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    • Metzger. J. V., Ed.; Wiley & Sons: New York.
    • Thiazole and its Derivatives; Metzger. J. V., Ed.; Wiley & Sons: New York. 1979.
    • (1979) Thiazole and Its Derivatives
  • 2
    • 84918117445 scopus 로고
    • Takeda Chem. Ind., Ltd. Fr. Patent 1,400,843, 1965
    • Takeda Chem. Ind., Ltd. Fr. Patent 1,400,843, 1965; Chem. Abstr. 1965, 63, 9922.
    • (1965) Chem. Abstr. , vol.63 , pp. 9922
  • 13
    • 0022367591 scopus 로고
    • The adduct 4 was isolated along with other secondary products from the reaction of the amino functionality with the acetylenic ester. See: Crank, G.; Khan, H. R. J. Heterocycl. Chem. 1985, 22, 1281-1284.
    • (1985) J. Heterocycl. Chem. , vol.22 , pp. 1281-1284
    • Crank, G.1    Khan, H.R.2
  • 39
    • 84962466172 scopus 로고    scopus 로고
    • note
    • These protons appear in the range of 5.95-6.68 ppm and, thus, at lower frequencies compared to the chemical shift of this proton in the thiazole ring (7.41 ppm).
  • 40
    • 37049126518 scopus 로고
    • The participation of dipolar intermediates in some of these reactions is supported by the high yields of fumarates obtained when the reaction is conducted in methanol, where a proton is available to quench the zwitterion. See: Acheson, R. M.; Brisdon, J. N.; Cameron, T. S. J. Chem. Soc., Perkin Trans. 1 1972, 968-975.
    • (1972) J. Chem. Soc., Perkin Trans. 1 , pp. 968-975
    • Acheson, R.M.1    Brisdon, J.N.2    Cameron, T.S.3
  • 41
    • 0001739662 scopus 로고
    • The reaction pathway to give the diastereomeric compounds 15 may involve the formation of the bent dipole 14g, which can easily equilibrate with 14g″ through the cumulenic 14g′. The (E)- and (Z)-15 adducts should be formed by migration of the hydrogen of the former C5 of the thiazole in 14g and 14g″ or, alternatively, from the allenic structure 16 by a tautomeric equilibrium. See: (a) Caramella, P.; Houk, K. N. Tetrahedron Lett. 1981, 22, 819-822.
    • (1981) Tetrahedron Lett. , vol.22 , pp. 819-822
    • Caramella, P.1    Houk, K.N.2
  • 46
    • 33745694624 scopus 로고
    • Müller, E., Ed.; G. Thieme Verlag: Stuttgart
    • (b) Seebach, D. In Houben-Weyl, Methoden der organischen Chemie; Müller, E., Ed.; G. Thieme Verlag: Stuttgart. 1971; Vol. IV/4, pp 418-419.
    • (1971) Houben-Weyl, Methoden der Organischen Chemie , vol.4 , Issue.4 , pp. 418-419
    • Seebach, D.1
  • 64
    • 0002728853 scopus 로고
    • Equation Presented
    • Reinhoudt has also proposed (see ref 21b) that the ring opening of thiabicyclo[3.2.0]hepta-3,6-dienes leading to the corresponding thiepines can be regarded as an electrocyclic symmetry-allowed disrotatory reaction of the dihydrothiophene ring analogous to that occurring in the isoelectronic bicyclo[4.2.0]octatriene which isomerizes rapidly to cyclooctatetraene. See: Glass, D. S.; Watthey, J. W. H.; Winstein, S. Tetrahedron Lett. 1965, 377-383. (Equation Presented)
    • (1965) Tetrahedron Lett. , pp. 377-383
    • Glass, D.S.1    Watthey, J.W.H.2    Winstein, S.3
  • 69
    • 1542508210 scopus 로고
    • Kharash, N., Ed.; Pergamon Press: New York
    • (b) Loudon, J. D. In Organic Sulfur Compounds; Kharash, N., Ed.; Pergamon Press: New York, 1961, pp 299-305.
    • (1961) Organic Sulfur Compounds , pp. 299-305
    • Loudon, J.D.1
  • 71
    • 84962466159 scopus 로고    scopus 로고
    • note
    • This value indicates that the C12 carbon atom presents an sp hybridization where the charge located at this center occupies a p atomic orbital. A similar value has been found in the transition state corresponding to the configuration inversion connecting two polar intermediates coming from the reaction of DMAD with 1-methylpyrrole (see ref 34).
  • 72
    • 84986492429 scopus 로고
    • In fact, INT is slightly higher in energy than TS2, probably as consequence of using the approximation of frozen geometries. See: (a) Bonaccorsi, R.; Cammi, R.; Tomasi, J. J. Comput. Chem. 1991, 12, 301-309.
    • (1991) J. Comput. Chem. , vol.12 , pp. 301-309
    • Bonaccorsi, R.1    Cammi, R.2    Tomasi, J.3
  • 79
    • 0001192473 scopus 로고    scopus 로고
    • Lipkowitz, K. B., Boyds, D. B., Eds.; VCH Publishers: New York
    • (b) Bartolotti, L. J.; Fluchichk, K. In Reviews in Computational Chemistry; Lipkowitz, K. B., Boyds, D. B., Eds.; VCH Publishers: New York, 1996; Vol. 7, pp 187-216.
    • (1996) Reviews in Computational Chemistry , vol.7 , pp. 187-216
    • Bartolotti, L.J.1    Fluchichk, K.2
  • 81


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