Journal of the American Chemical Society p. 7122 - 7133 (1981)
Update date:2022-08-03
Topics:
Paquette, Leo A.
Bellamy, Francois
Wells, Gregory J.
Boehm, Michael C.
Gleiter, Rolf
Product and relative reactivity data have been obtained for the photooxygenation, epoxidation, cyclopropanation, oxymercuration, and hydroboration of three differently substituted (aryl) 2-methylbenzobicyclo<2.2.2>octadienes.Syn stereoselectivity was observed in every case, with the level of syn attack being highest with the tetrafluoro derivative 2c (except in the Simmons-Smith reaction where a single isomer was produced in every case).Only small differences in rate were seen with a given reagent.Electronic interactions in these molecules were explored by photoelectron spectroscopy and MINDO/3 calculations.These combined tools served to show that through-space interaction is absent in these molecules.However, through-bond coupling in 2a and 2b leads to olefinic ?-bond disrotation.The relative importance of this effect as well as long-range Coulomb and charge-transfer interactions is discussed.A connection between such subtle electronic influences and stereoselectivity is established, although prevailing steric effects do serve to compress somewhat the syn/anti range available to these systems.
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