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Synlett 2005(19): 2911-2914  
DOI: 10.1055/s-2005-918959
LETTER
© Georg Thieme Verlag Stuttgart · New York

Stability Relationships in Bicyclic Ketones

Heather L. Gordon*, Stanley Freeman, Tomas Hudlicky*
Department of Chemistry and Centre for Biotechnology, Brock University, St. Catharines, Ontario L2S 3A1, Canada
e-Mail: gordonh@brocku.ca; e-Mail: thudlicky@brocku.ca; e-Mail: Stanley_freeman@merck.com;
Further Information

Publication History

Received 13 August 2005
Publication Date:
27 October 2005 (online)

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Abstract

Calculated energy differences between cis- and trans-fused bicyclic ketones are provided for bicyclo[3.3.0]octanones, bicyclo[4.3.0]nonanones, bicyclo[5.3.0]decanones, bicyclo[6.3.0]undecanones and the corresponding hydrocarbons with and without angular methyl groups. The calculations were performed for HF/6-31G* and MP2/6-31G* optimized geometries. The latter were used for subsequent single-point energy MP2/6-311G* calculations. Whenever possible, the calculated energy differences were compared with experimental data and found to correspond well. The ­results of the calculations provide a complete picture of expected energetic differences in bicyclic ketone series and will be useful in both instruction and synthetic planning.

Key words

bicyclo[3.3.0]octanones - bicyclo[4.3.0]nonanones - calculated energy differences

    References

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1

Present address: Merck Research Laboratories, Rahway, NJ, USA. E-mail address: Stanley_freeman@merck.com.

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Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, J. A. Jr.; Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian 03, Revision B.03, Gaussian, Inc., Pittsburgh PA, 2003.

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All quantum mechanical calculations were carried out using Gaussian03 (see ref. 8). Summary of calculations of all molecules in Table [1] , Table [2] , Table [3] , and Table [4] , including all levels of theory, is available on request.