Conclusions
-
1.
cis-Alloocimene adds acrylonitrile to give two stereoisomeric adducts, which exist in a half-chair conformation. Based on PMR spectra, one of the stereoisomers has a quasiaxial methyl group and pseudoequatorial nitrile and isopropylidene groups, while the other stereoisomer has a quasi-axial isopropylidene substituent and equatorial nitrile and methyl groups.
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2.
Dichlorocyclopropanation of these adducts occurs from the sterically less hindered side of the molecules, with the formation, from one of the stereoisomers, of a cycloaddition product at the exocyclic double bond, and two stereoisomeric cycloaddition products at the two double bonds with a cis orientation of the cyclopropane ring and the CN group; the other stereoisomer, on the other hand, gives two stereoisomeric cycloaddition products at the two double bonds with a trans orientation of the cyclopropane ring and CN-group.
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Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1087–1093, May, 1988.
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Arbuzov, B.A., Ratner, V.V., Danilova, O.I. et al. PMR study of the three-dimensional structure of stereoisomeric adducts of cis-alloocimene with acrylonitrile and their cyclization products with dichlorocarbene. Russ Chem Bull 37, 951–956 (1988). https://doi.org/10.1007/BF00957068
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DOI: https://doi.org/10.1007/BF00957068