Deamination of endo-and exo-2-aminobicyclo[3.1 .O] hexanes (7) and (8) and solvolysis of the corresponding 2-chloro-compounds (1) and (2) yield very similar ratios of products showing the intervention of a common 2-cation. Rate studies of solvolysis of 2-substituted bicyclohexyl derivatives and some 5-methyl-substituted compounds indicate that the normal rate-enhancing effect of the cyclopropyl group is due to delocalisation of the symmetrical homoallyl type for endo-and exo-leaving groups. Deuterium scrambling from the 5-position was not observed in solvolysis of chlorides (1) and (2). Leeds LS2 9JT 1 Preliminary communication, P. R. Brook, R. M. Ellam, and A. S. Bloss, Chem. Cornm., 1968, 425. p. 1295; (d) see also M. Hanack and H. J. Schneider, Angew. Chem. Internat. Edn., 1967, 6, 666; (e) B. Capon, Quart. Rev., 1964, 18, 45. charge and the neighbouring cyclopropyl group. Z-Substituted bicyclo[3.1 .O]hexanes were readily accessible compounds for study.A recent report prompts publication now. Tosyl esters of the epimeric bicyclo[3.1 .O]hexan-2-01s (4) and (5) were found too reactive for convenient isolation.g The corresponding endo-(1) and exo-Z-chlorobicyclohexanes (Z), were then chosen, as g.1.c. techniques could be used for analysis and purification (although not without difficulty).Reduction of bicyclohexan-%one (3) with sodium borohydride gave a mixture of the epimeric 2-alcohols containing 93% eutdo-derivative (4) .7 This mixture on of work closely related to our own
4ssumption of an initial crosswise approach of cyclopentadiene and a keten, combined with simple frontier orbital considerations, leads to a prediction of stereochemistry in the electrocyclic addition which has been confirmed by experiment.
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