Self-assembly of frame structures. 10. Stereochemistry of 2,5-dioxabicyclo [2.2.1]heptane-3,6-dione

Authors

  • И. B. Выстороп Institute of Chemical Physics at Chernogolovka, Russian Academy of Sciences, Chernogolovka 142432
  • А. Раук Department of Chemistry, University of Calgary, Alberta
  • К. Хейм Department of Chemistry, College of Sciences, Autonomous University of Barcelona, Bellaterra 08193
  • И. Динарес Laboratory of Organic Chemistry, College of Pharmacy, University of Barcelona, Barcelona 08028
  • Р. Г. Костяновский N. N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, Moscow 117977

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 (1R,4R)-enantiomer (the dihedral angles of the lactone bridges are φ0 = 2.6°). According to MM2(91) and MM3(92) calculations, (1R,4R)-1 exists as the synchro(+, +)-A-twist (φ0 = 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.

How to Cite
Vystorop, I. V.; Rauk, A.; Jaime, C.; Dinarés, I.; Kostyanovskii, R. G. Chem. Heterocycl. Compd. 1995, 31, 1280. [Khim. Geterotsikl. Soedin. 1995, 1479.]

For this article in the English edition, see DOI https://doi.org/10.1007/BF01168620

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Published

1995-11-25

Issue

No. 11 (1995)

Section

Original Papers