On the reactivity of 1-amino-3-siloxy-1,3-dienes: Kinetics investigation and theoretical interpretation

Journal of Organic Chemistry

Volumn 64, Issue 21, 1999, Pages 8045-8047

  Kozmin, Sergey A ^a   Green, Michael T ^a   Rawal, Viresh H ^a  

^a UNIVERSITY OF CHICAGO   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKADIENE;

ARTICLE; CALCULATION; CHEMICAL REACTION KINETICS; CHEMOREACTIVITY; REACTION ANALYSIS; THEORY;

EID: 0032721874     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo990923g     Document Type: Article

References (24)

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4. For l,3-bis(dimethylamino) dienes, see: (a) Gomper, R.; Sobotta, R. Tetrahedron Lett. 1979,921. (b) Gomper, R.; Heinemann, U. Angew. Chem., Int. Ed. Engl. 1980, 19, 216.
5. For l-amino-3-siloxy dienes, see: (a) Smith, A. B., HI; Wexler, B. A.; Tu, C.-Y.; Konopelski, J. P. J. Am. Chem. Soc. 1985,107, 1308. (b) Comins, D. L.; Al-awar, R. S. J. Org. Chem. 1992, 57, 4098. (c) Schlessinger, R. H.; Pettus, T. R. R. J. Org. Chem. 1994, 59, 3246.
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7. Kozmin, S. A.; Rawal, V. H. J. Am. Chem. Soc. 1998,120,13523.
8. (a) Baldwin, S. W.; Greenspan, P.; Alaimo, C.; McPhail, A. T. Tetrahedron Lett. 1991, 32, 5877. (b) Danishefsky, S.; Kitahara, T.; Yan, C. F.; Morris, J. J. Am. Chem. Soc. 1979,101, 6996. (c) Vorndam, P. E. J. Org. Chem. 1990, 55, 3693.
9. See the Supporting Information for a second-order rate plot.
10. 3-treated chloroform is used.
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15. The TBS-protected Danishefsky's diene (2b) was conveniently prepared using the KHMDS/TBSC1 protocol used for the synthesis of l-amino-3-siloxy-1,3-dienes (see ref 6c).
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18. (a) In the case of simple 1-dialkylamino-substituted dienes, the [4 + 2] mechanism is usually proposed: Koikov, L. N.; Terentev, P. B.; Gloriozov, I. P.; Bundal, Y. G. J. Org. Chem. USSR (Engl. Transl.) 1984,20,832. (b) However, so far very little evidence has been provided experimentally to support this concept: Gouesnard, J. P.; Martin, G. J.; Blain, M. Tetrahedron 1974,30,151. (c) The possibility of a stepwise mechanism has also been suggested: Sustmann, R.; Rogge, M.; Nuchter, U.; Bandmann, H. Chem. Ber. 1992, 125, 1647.
19. A recent ab initio study by Sustmann et al. demonstrated that the transition states for the Diels-Alder reactions of 1-amino-1,3-butadiene with several cyano-substituted dienophiles correspond to a [4 + 2] cycloaddition pathway: Sustmann, R.; Sicking, W. J. Am. Chem. Soc. 1996, 118, 12562.
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22. GAUSSIAN 94: Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Gill, P. M. W.; Johnson, B. J.; Robb, M. A.; Cheeseman, J. R.; Keith, T. A.; Peterson, G. A.; Montgomery, J. A.; Raghavachari, K.; AlLatham, M. A.; Zakrzewski, V. G.; Ortiz, J. V.; Foresman, J. B.; Cioslowski, J.; Stefanov, B. B.; Nanayakara, A.; Challacombe, M.; Peng, C. Y.; Ayala, P. Y.; Chen, W.; Wong, M. W.; Andres, J. L.; Replogie, E. S.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Binkley, J. S.; Defrees, D. J.; Baker, J.; Stewart, J. J. P.; Head-Gordon, M.; Gonzalez, C.; Pople, J. A. Gaussian, Inc., Pittsburgh, PA, 1995.
23. See the Supporting Information.
24. Craig, D.; Shipman, J. J.; Fowler, R. B. J. Am. Chem. Soc. 1961, 83, 2885.