452-61-9Relevant academic research and scientific papers
Homolytic reactions of homocubane and basketane: Rearrangement of the 9-basketyl radical by multiple β-scissions
Binmore, Gavin T.,Della, Ernest W.,Elsey, Gordon M.,Head, Nicholas J.,Walton, John C.
, p. 2759 - 2766 (2007/10/02)
Methods are described for the synthesis of 9-hydroxy- and 9-bromopentacyclo[4.3.0.02,5.03,8.04,7]nonane (homocubane derivatives) and for the same derivatives of pentacyclo[4.4.0.02,5.03,8.04,7/s
The preparation and fate of cubylcarbinyl radicals
Eaton, Philip E.,Yip, Yu Chi
, p. 7692 - 7697 (2007/10/02)
The cubylcarbinyl radical has been generated from cubylcarbinyl bromide and from the N-hydroxy-2-pyridinethaione ester of cubylacetic acid under various conditions favoring hydrogen-atom transfer to the radical. Only when selenophenol in high concentration is used as the hydrogen donor is any methylcubane formed. Otherwise the cubylcarbinyl radical rearranges. There is no evidence of a 1,2-shift into the homocubyl system. Instead, one, two, or three bonds of the cubane nucleus cleave, leading to a variety of olefinic products. For the most part, these have been characterized. A mechanistic scheme accounting for their formation is presented; sequential σ-bond breaking occurs regioselectively, favoring processes in which there is good overlap between the radical orbital and that of the breaking bond. The distribution of products is shown to depend qualitatively on the time the radical intermediates are let live, that is, on the concentration and effectiveness of the hydrogen atom transfer agent. From product distributions, the rate constant for ring cleavage of cubylcarbinyl radical is calculated to be at least 2 × 1010 s-1, substantially greater than that of any radical derived to date from a saturated hydrocarbon system. Methodology is given for the synthesis of cubylcarbinol, cubylacetic acid, 1,4-bis(hydroxymethyl)cubane, methylcubane, and a variety of other new cabane compounds.
Hydrogenolysis of Small Cycloalkanes, XIII - Hydrogenation of Homucubane Derivatives
Osawa, Eiji,Schneider, Ingrid,Toyne, Kennet J.,Musso, Hans
, p. 2350 - 2361 (2007/10/02)
Two dihydro products 5a and 7a are formed by hydrogenation of homocubane (6a) with Pd-, Pt-, and Rh-catalysts.Only the unsymmetric 7a reacts further to give twistbrendane (8a).In addition, ca. 20percent brendane (11a) is obtained by hydrogenation of homocuneane (9a), which is formed from 6a by rearrangement on the catalyst.The yield of the symmetric dihydro product 5b is raised up to 40percent in the case of hydrogenation of the ethylene acetal 6b of the 9-ketone on Rh/Al2O3.With the ester 6d no 5d is obtained but 7d and 8d only.
The 13C and 1H N.M.R. Spectra of Homocubane, Norsnoutane and their 9-Keto- and 9,9-Ethylenedioxy-derivatives, and a Novel Route to Functionalised Brendanes
Hamlin, John E.,Toyne, Kenneth J.
, p. 2731 - 2736 (2007/10/02)
The 13C and 1H n.m.r. spectra of homocubane (pentacyclo2,5.03,8.04,7>nonane) (5), norsnoutane (pentacyclo2,4.03,8.05,7>nonane) (12) and their 9-keto- and 9,9-ethylenedioxy-derivatives have been analysed using deuterium labelling.The protons α to the carbonyl and acetal group and the carbon atoms bearing these protons shown unusual absorptions.The substituent effects in homocubanes and norbornanes are similar and no significant additional effect is apparent in the cage structure; the effect of the endo-annulated cyclopropane rings in the norsnoutanes is discussed.The hydrochloric acid-catalysed rearrangement of 9,9-ethylenedioxypentacyclo2,4.03,8.05,7>nonane (10) gives the brendane derivative, exo-2-chlorotricyclo3,7>non-4-en-8-one (16).
