Orbital control of stereochemistry in acid-catalysed addition reactions of endo -tricyclo[3.2.1.02,4]0ct-6-ene |
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| Authors: | Merle A. Battiste James M. Coxon Gregory W. Simpson Peter J. Steel Alan J. Jones |
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| Affiliation: | Chemistry Department, University of Florida, Gainesville FL 32611, U.S.A.;Chemistry Department, University of Canterbury, Christchurch New Zealand;Chemistry Department, The Faculties, Australian National University, Canberra Australia 2601 |
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| Abstract: | The reaction of endo-tricyclo[3.2.1.02,4]oct-6-ene 1 with methanol in the presence of catalytic amounts of toluene-p-sulphonic acid has been shown to give 2-exo- and endo-methoxybicyclo[3.2.1]oct-3-ene (2c) and (2d) and 2-endo-methoxybicyclo[3.2.1]oct-6-ene (13). The formation of 2-exo- methoxybicyclo[3.2.1]oct-3-ene (2c), the major product of reaction, has been probed by deuterium labelling experiments and a series of 6-exo-7-exo- dideuterobicyclo[3.2.1]oct-3-enes synthesised for 2H, 1H and 13C NMR spectral analysis in order unambiguously to determine the stereochemistry of proton attack on endo-tricyclo[3.2.1 02,4]oct-6-ene (1). The formation of 2-exo-methoxybicyclo[3.2.1]oct-3-ene (2c) has been determined to involve corner protonation of the cyclopropyl moiety and skeletal rearrangement to an allylic cation with a small but measurable memory effect |
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