15840-67-2Relevant academic research and scientific papers
Cyclisation of 5-Bromomethyl-cycloheptene and -cyclo-octene: a New Route to Bicyclooctanes and Bicyclononanes
MacCorquodale, Finlay,Walton, John C.
, p. 347 - 352 (2007/10/02)
Reduction of 5-(bromomethyl)cycloheptene with tributyltin hydride gave bicyclooctane; similar reduction of 5-(bromomethyl)cyclo-octene gave bicyclononane together with some bicyclononane.The cyclohept-4-enylmethyl radical intermediate
Formation of Bicyclooctane, Bicyclononane, and Bicyclononane by Transannular Radical Cyclisations
MacCorquodale, Finlay,Walton, John C.
, p. 1456 - 1457 (2007/10/02)
Cyclohept-4-enylmethyl radicals undergo transannular cyclisation to give bicyclooctane; likewise, bicyclononane and bicyclononane are obtained from cyclo-oct-4-enylmethyl radicals.
Evidence for Single Electron Transfer in the Reactions of Lithium Dimethylcuprate with Alkyl Halides
Ashby, E. C.,Coleman, David
, p. 4554 - 4565 (2007/10/02)
A variety of methods have been utilized to explore the occurence of radical intermediates and free-radical chain processes initiated by electron transfer in the reactions of lithium dimethylcuprate with alkyl halides.The effect of leaving group, nature of the cuprate species, and ratio of cuprate to substrate, solvent, hydrogen atom donor, and other additives on the rate of and product distribution were investigated by using a cyclooctenyl radical probe.The presence of significant amounts of radicals strongly supports single electron transfer (SET) as a major pathway for the reaction of secondary iodides with LiCuMe2.There is some evidence of single electron transfer also accurring with secondary bromides, but tosylates appear to be reacting entirely by a SN2-like pathway.The role of dicyclohexylphosphine (DCPH) as an additive in the reaction was investigated with the result that it was shown to be capable of behaving in a unique manner depending on wheter the substrate is an alkyl iodide or bromide.The product distribution, rate, and effect of p-dinitrobenzene on the reaction of 5-iodo-1-cyclooctene were compared with three other probes and the results demonstrate that at least three reaction pathways are involved to varying degrees.These pathways could involve the initiation of free radicals or radical anion (SRN1) chain processes. these studies also demonstrate how changes in the substrate can alter the predominant reaction pathways that are followed.
Electrophilic Cleavage of Cyclopropanes. Acetolysis of Bicyclic and Tricyclic Cyclopropanes
Wiberg, Kenneth B.,Kass, Steven R.,Meijere, Armin de,Bishop, K. C.
, p. 1003 - 1007 (2007/10/02)
The acetolysis of a series of bicycloalkanes and propellanes has been studied.The effect of ring strain, caused by changing ring size or introducing a trans-ring fusion, on the rate and products of the reaction has been examined.No correlation was found between rates of acetolysis and strain energy relief, but with the exception of propellane, there is a rough correlation with ionization potentials.The degree of polarization of the C-C bonds in the presence of a proton correlates very well with reactivity and is a controlling factor for the acetolysis rates.The importance of the energies of unoccupied orbitals with the appropriate symmetry in controlling electron polarization is shown by the large difference in rate of reaction between - and propellanes.
