42402-81-3Relevant articles and documents
Conversion of Saturated Ketones into 2-Lithiodienes via N,N-Bis-Tosylhydrazone Derivatives
Magnus, Philip,Roe, Michael B.
, p. 5479 - 5482 (2007/10/02)
Saturated N-tosylhydrazones can be converted into 2-lithiodienes via N,N-bis-tosylhydrazones and elimination to an α,β-unsaturated N-tosylhydrazone, followed by the Shapiro reaction.
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.
Generation of Bicycloheptatrienes
Billups, W. E.,Reed, Larry E.,Casserly, Edward W.,Lin, L. P.
, p. 1326 - 1333 (2007/10/02)
Derivatives of bicycloheptatriene have been generated in solution by the base-induced dehydrochlorination of gem-dichlorocyclopropanes.Reaction of 7,7-dichlorodibenzobicycloheptane with potassium tert-butoxide in tetrahydrofuran at 0 deg C gives mainly products derived from solvent incorporation by carbene insertion.Evidence that the carbene results from rearrangement of the bicycloheptatriene derives from the successful interception of the bicycloheptatriene with nucleophile (MeS-). endo-7-Chlorodibenzobicycloheptane failed to reactwith potassium tert-butoxide in tetrahydrofuran.Generation of benzobicycloheptatrienes was also accomplished via the base-induced dehydrochlorination of gem-dichlorocyclopropanes. 1-Methylbenzobicycloheptatriene gives products derived from multiple carbene-carbene rearrangements.In contrast, nonannelated methylbicycloheptatrienes generated by the dehydrochlorination route give only carbene-derived products resulting from the initially produced bicycloheptatriene.
