29073-66-3Relevant academic research and scientific papers
Rearrangement of Bicyclooct-2-en-6-yl and Benzobicyclooctenyl Cations
Kirmse, Wolfgang,Moench, Dietmar
, p. 1287 - 1294 (2007/10/02)
The ketones 9, 27, and 51 were prepared by modified or novel routes.The analogous tosylhydrazones 10, 28, and 52 were photolyzed in 0.5 N NaOH to generate the carbocations 15, 34, and 53, respectively, by way of diazonium precursors. 2,3-Unsaturati
Photolytic Cleavage of Remote Functional Groups in Polyfunctional Molecules. Photolysis of exo- and endo-Benzobicycloocten-2-yl Chloride
Morrison, Harry,Muthuramu, Kayambu,Pandey, Genesh,Severance, Daniel,Bigot, Bernard
, p. 3358 - 3363 (2007/10/02)
The aryl-induced photolytic cleavage of a remote C-Cl bond, earlier reported for the 2-position in the benzonorbornenyl series, is extended to the 2-position of the title compounds (exo-BBCl and endo-BBCl).Cleavage with 254-nm excitation is an efficient reaction (ψdis = 0.45 and 0.005, exo and endo, respectively), involving the aryl singlet excited state.Radical and carbocation derived products are observed (eq.3), with the latter including an olefin (8), a cyclopropane (9), and rearranged ethers (10 and 13) attributed to "hot" cation intermediates.The rate constants for C-Cl cleavage sre as follows: exo 1.1*109 s-1; exo 2.2.2>, 3.8*108 s-1; endo , 1.7*106 s-1; endo , 2.7*105 s-1.These rates are discussed within the context of previously proposed mechanisms.
Electronic Control of Stereoselectivity. 9. The Stereochemical Course of Electrophilic Additions to Aryl-Substituted Benzobicyclooctadienes
Paquette, Leo A.,Bellamy, Francois,Wells, Gregory J.,Boehm, Michael C.,Gleiter, Rolf
, p. 7122 - 7133 (2007/10/02)
Product and relative reactivity data have been obtained for the photooxygenation, epoxidation, cyclopropanation, oxymercuration, and hydroboration of three differently substituted (aryl) 2-methylbenzobicyclooctadienes.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.
