“…The second transannular bridge formation in I occurred in the cross (N-type) manner leading to cation II , which was then captured by bromide ion approaching from the sterically less hindered “endo-side” to give dibromide 17 . It is interesting to note that the mode of the first transannular bridge formation (parallel, U-type) is in line with the transannular additions of analogous systems involving norbornene moiety and the second ( I → II ) parallels the bromination reactions of triene 13 (cross, N-type) shown by eq 4 and other systems having an endo,endo -diethenonaphthalene skeleton. , 2 ORTEP drawing of compound 17 . 3 …”
“…The second transannular bridge formation in I occurred in the cross (N-type) manner leading to cation II , which was then captured by bromide ion approaching from the sterically less hindered “endo-side” to give dibromide 17 . It is interesting to note that the mode of the first transannular bridge formation (parallel, U-type) is in line with the transannular additions of analogous systems involving norbornene moiety and the second ( I → II ) parallels the bromination reactions of triene 13 (cross, N-type) shown by eq 4 and other systems having an endo,endo -diethenonaphthalene skeleton. , 2 ORTEP drawing of compound 17 . 3 …”
“…Comparable irradiation of 23 rigorously determined, we favor the exo form since continued exposure to light did not result in (2 + 2) cycloaddition as anticipated for the endo isomer. When pyrolyzed above 575 °C, both 16 and 23 were converted to a mixture of benzylcyclopentadiene isomers (26).…”
mentioning
confidence: 61%
“…1H NMR analysis indicated the first peak to be unreacted starting materials and the fourth to be the known hydrocarbon 21. 23 The second component remains unidentified. The major product was 20: ¿Me4SiCDCi3 2.4-2.6…”
Section: Methodsmentioning
confidence: 99%
“…When pyrolyzed above 575 °C, both 16 and 23 were converted to a mixture of benzylcyclopentadiene isomers (26). 27 Importantly, the desired tetraene (13) was obtained upon thermolysis of 23 at 380 °C in a flow system (gas phase, N2 as carrier gas). Although a single product was formed under these conditions, the conversion realized was only 66%.…”
“…A mixture of N-type and U-type products was obtained in the electrophilic addition reaction of bromine to TCTD molecule (Scheme 4). 2,36 The geometry and the electronic structure of the TCTD molecule were investigated using the B3LYP/6-311G(d,p) and B3LYP/6-311+ G(d,p) methods and the structure of the molecule was also investigated in detail. In order to determine the structures and relative stabilities of the predicted cationic intermediates (bridged, N-and U-type cations) (Scheme 5) formed in the addition reaction, their full geometry optimization was performed at the B3LYP/6-311G(p,d) level and the total energies (E tot ) were also calculated.…”
Transannular electrophilic addition reaction of halogens to face-to-face(juxtaposed) double bonded strained alkenes were theoretically investigated. General rules that allow us to stipulate the factors that direct the main steps of the energy hypersurface of reactions as well as the products were established. Direction of the reaction flow is determined by direction of intramolecular skeletal isomerisation of cyclic-bridged halogenium cation and isomerisation takes place to create a more stable skeletal structure. Stability of resultant skeletal structure is determined by the number of σ bonds between isolated double bonds of the alkene and bonding-type of double bonds (N-and U-type). When the number of σ bonds between double bonds of the alkene is three (m = 3), the reaction takes place to predominantly give an N-type product, and when four (m = 4), N-and U-type products are formed. Structure and stability of cation intermediates (bridged, N-and U-type cations) of electrophilic addition reaction of homohipostrofen molecule, whose double bonds were linked by three σ bonds, with bromine were investigated by DFT methods in detail. Also the addition reaction of endo,endo-tetracyclo[6.2.2.2 3,6 .0 2,7 ]tetradeca-4,9-dien molecule, whose double bonds were linked by four σ bonds, with bromine were investigated by quantum chemistry.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
