Abstract
By optimization of the geometry of 2, 5-dioxabicyclo[2. 2.1]heptane-3.6-dione (1) with an ab initio (RHF/6-31 G') calculation, we have found that a single synchro(+, +)-twist form (A) corresponds to the (1 R,4R)-enantiomer (the dihedral angles of the lactone bridges areϕ 0 = 2.6°). According to MM2(91) and MM3(92) calculations, (1R,4R)-1 exists as the s-ynchro(+, +)-A-twist (ϕ 0 = 3.9°) and the synchro(-, -)-B-twist (ϕ = -3.8°) forms, respectively. Investigating the torsional energy surface of the dilactone 1 (MM2(91)), we found only the (1R,4R,P)-diastereomeric form (A), which is stabilized compared with the (1R,4P,M) form (B) (probably as a result of the more preferred dipole-dipole interaction of the carbonyl groups). According to the calculated puckering coordinates, the five-membered and six-membered moieties of the bicycle 1 are flattened compared with norbornane.
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References
R. G. Kostyanovskii, Yu, I. Él'natanov, O. N. Krutius, and V. N. Voznesenskii, Izv. Akad. Nauk, Ser. Khim., No. 2, 327 (1995).
A. Rauk, C. Jaime, I. V. Vystorop, V. M. Anisimov, and R. G. Kostyanovsky, J. Mol. Struct. (Theochem),342, 93 (1995).
R. G. Kostyanovskii, V. P. Leshchinskaya, Yu. I. Él'natanov, A. É. Aliev, and I. I. Chervin, Izv. Akad. Nauk SSSR, Ser. Khim., No. 2, 408 (1989).
R. G. Kostyanovskii, I. V. Vystorop, A. E. Aliev, Yu. I. ÉI'natanov, V. N. Voznesenskii, V. I. Zav'yalov, and R. A. Karakhanov, Izv. Akad. Nauk SSSR, Ser. Khim., No. 4, 891 (1989).
I. V. Vystorop, Yu. I. Él'natanov, and R. G. Kostyanovskii, Izv. Akad. Nauk, Ser. Khim., No. 7, 1591 (1992).
I. V. Vystorop, A. B. Zolotoi, V. M. Anisimov, V. G. Kartsev, and R. G. Kostyanovskii, Izv. Akad. Nauk, Ser. Khim., No. 7, 1601 (1992); I. V. Vystorop, G. V. Shustov, A. Rauk, and R. G. Kostyanovsky, Mendeleev Commun., No. 3, 97 (1994).
W. Schweizer and J. Dunitz, Helv. Chim. Acta,65, 1547 (1982).
K. B. Wiberg and R. F. Waldron, J. Am. Chem. Soc.,113, 7697, 7705 (1991).
N. L. Allinger, Pure Appl. Chem.,54, 2515 (1982).
C. Jaime, R. M. Ortuño, and J. Font, J. Org. Chem.,51, 3946 (1986); C. Jaime, C. Segura, I. Dinarés, and J. Font, J. Org. Chem.,58, 154 (1993).
N. L. Allinger, Z. S. Zhu, and K. Chen, J. Am. Chem. Soc.,114, 6120 (1992). (Version MM3(92) program is available to academic users only from the Quantum Chemistry Program Exchange (Q.C.P.E.), University of Indiana, Bloomington, IN 47405 USA.)
N. L. Allinger, II. J. Geise, W. Pyckhout, L. A. Paquette, and J. C. Gallucci, J. Am. Chem. Soc.,111, 1106 (1989).
L. Doms, L. van den Enden, H. J. Geise, and C. van Alsenoy, J. Am. Chem. Soc.,105, 158 (1983).
A. Yokozeki and K. Kuchitsu, Bull. Chem. Soc. Jpn.,44, 2356 (1971).
J. F. Chiang, C. F. Wilcox, and S. H. Bauer, J. Am. Chem. Soc.,90, 3149 (1968).
C. van Alsenoy, J. N. Scarsdale, and L. Schafer, J. Comput. Chem.,3, 53 (1982).
C. R. Castro, R. Dutler, A. Rauk, and H. Wieser, J. Mol. Struct. (Theochem),152, 241 (1987).
K. B. Wiberg, R. F. W. Bader, and C. D. H. Lau, J. Am. Chem. Soc.,109, 985, 1001 (1987).
M. J. Frisch, G. W. Trucks, M. Head-Gordon, P. M. W. Gill, M. W. Wong, J. B. Foresman, B. G. Johnson, H.B. Schlegel, M. A. Robb, E. S. Replogle, R. Gomperts, J. L. Andres, K. Raghavachari, J. S. Binkley, C. Gonzalez, R. L. Martin, D. J. Fox, D. J. Defrees, J. Baker, J. J. P. Stewart, and J. A. Pople, “Gaussian 92, Revision B,” Gaussian, Inc., Pittsburgh PA (1992).
Version MM2(91) program. Available to academic users from Q. C. P. E., University of Indiana, Bloomington, IN 47405 USA.
N. L. Allinger, J. Am. Chem. Soc.,99, 8127 (1977).
N. L. Allinger, Y. H. Yuh, and L. H. Lii, J. Am. Chem. Soc.,111, 8551, 8566, 8576 (1972).
C. Altona and M. Sundaralingam, J. Am. Chem. Soc.,94, 8205 (1972); C. Altona, Rec. Trav. Chim.,101, 413 (1982).
N. S. Zefirov and V. A. Palyulin, Dokl. Akad. Nauk SSR,252, 111 (1980).
“IUPAC tentative rules for the nomenclature of organic chemistry. Section E. Fundamental stereochemistry,” I. Org. Chem.,35, 2849 (1970).
L. Norskov-Lauritsen, H.-B. Burgi, P. Hofmann, and H. Schmidt, Helv. Chim. Acta,68, 76 (1985).
K. Tamagawa and R. L. Hilderbrand, J. Phys. Chem.,87, 5508 (1983).
J. Mathiev and R. Panico, Reaction Mechanisms in Organic Chemistry [in French], Hermann (1972), Chapter 3, Section 3.2.2.
M. J. S. Dewar and W. Thiel, J. Am. Chem. Soc.,99, 4899 (1977).
M. J. S. Dewar, E. G. Zoebisch, E. F. Healy, and J. J. P. Stewart, J. Am. Chem. Soc.,107, 3902 (1985).
J. J. P. Stewart, J. Comput. Chem.,10, 209 (1989).
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Institute of Chemical Physics at Chernogolovka. Russian Academy of Sciences, Chernogolovka, Moscow Oblast 142432. Department of Chemistry, University of Calgary, Alberta, Canada T2N 1N4. Department of Chemistry, College of Sciences, Autonomous University of Barcelona, Bellaterra 08193, Spain. Laboratory of Organic Chemistry, College of Pharmacy, University of Barcelona, Barcelona 08028, Spain. N. N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, Moscow 117977. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1479-1488, November, 1995.
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Vystorop, I.V., Rauk, A., Jaime, C. et al. Self-assembly of frame structures. 10. Stereochemistry of 2,5-dioxabicyclo [2.2.1]heptane-3,6-digne. Chem Heterocycl Compd 31, 1280–1288 (1995). https://doi.org/10.1007/BF01168620
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DOI: https://doi.org/10.1007/BF01168620