Article citationsMore>>
M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. A. Montgomery, Jr., T. Vreven, K. N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A. AlLaham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, C. Gonzalez and J. A. Pople, “Gaussian 03 Revision E.01,” Gaussian 03, Revision E.01, Gaussian, Inc., Wallingford, 2004.
has been cited by the following article:
-
TITLE:
Computational Study of the Cyclization of 5-Hexenyl, 3-Oxa-5-Hexenyl and 4-Oxa-5-Hexenyl Radicals
AUTHORS:
Albert R. Matlin, Matthew C. Leyden
KEYWORDS:
Radical Cyclizations; Activation Energies; UB3LYP; UCCSD (T)
JOURNAL NAME:
International Journal of Organic Chemistry,
Vol.3 No.3,
August
27,
2013
ABSTRACT: The intramolecular cyclization of 5-hexenyl radicals continues to be an important synthetic method for the construction of five-membered rings. The synthetic utility arises from the high degree of regioselectivity to give predominantly cyclopentyl products in high yield under mild conditions. Recently we reported product cyclization studies on 4-oxa perturbed 5-hexenyl radical. In this paper, we report our results from a computational study (UB3LYP and UCCSD (T)) of the cyclization of a series of 5-hexenyl and 3-and 4-oxa-5-hexenyl radicals. Three highly conserved cyclization tran-sitions states (exo-chair, exo-boat and endo-chair) were located for 10 acyclic radicals. Activation energies were calcu-lated for the three modes of cyclization for each radical. Calculated values for the exo/endo cyclization ratios had a high level of agreement with experiment and predictions were offered for two cases that have not been experimentally tested. The increased percentage of exo-cyclization with 3-and 4-oxa substitution is the result of an increase in the energy dif-ference between the exo-and endo-chair transition states compared to the hydrocarbon systems. The decreased rate of cyclization of the 4-oxa compounds is primarily due to the stabilization of the initial acyclic radical by the vinyl ether linkage. The increase in the rate of cyclization with 3-methyl substitution is due to the increased conformational energy of the starting acyclic radical.
Related Articles:
-
Casimir Komenan
-
Moawwad E. A. El-Mikkawy
-
Masanori Ono, SaangJoon Baak
-
Mohammad Reza Farahani, Wei Gao
-
Zheng Yuan