Theoretical Investigation of Electrophilic Transannular Addition Reactions of Bromine to Face-to-Face (Juxtaposed) Double Bonds in Strained Polycyclic Hydrocarbons.

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[6.2.2.23,6.02,7]tetradeca-4,9-dien molecule, whose double bonds were linked by four σ bonds, with bromine were investigated by quantum chemistry.

Synthesis of a new 1,2,3,4,5-pentasubstituted cyclohexanol and determining its stereochemistry by NMR spectroscopy and quantum-chemical calculations.

The presence of substituents in cyclohexane can influence to the ratio of conformers; for some cases, the boat form is preferable. The new six-membered cyclohexanol derivative 2 has been obtained by the synthesis of (E)-1-(bromophenyl)-3-phenylpropen-2-one (1). The NMR and quantum-chemical conformational analysis for the 2 have carried out, and its possible mechanism of formation was given. Copyright © 2015 John Wiley & Sons, Ltd.

DFT investigation of the mecahanism and stereochemistry of electrophilic transannular addition reaction of bromine to tricyclo[4.2.2.02,5]deca-3,7-diene.

Full geometric optimization of tricyclo[4.2.2.02,5]deca-3,7-diene (TDD) has been done by DFT/B3LYP methods and the structure of the molecule was investigated. Cyclobuten double bond (I) of molecule is syn pyramidalized, and bicyclookten double bond (II) is also exo pyramidalized. The double bond (I) is more pyramidalized than the double bond (II) and it has higher reactivity. The TDD-Br2 system has been investigated by B3LYP/6-311++G(d,p) method and their stable configurations have been determined. The cationic intermediates and products obtained as a result of the addition reaction has been studied using B3LYP/6-311G(d,p) and B3LYP/6-311++G(d,p) methods. Bridged bromonium cation is more stable than U-type cation. Considering that the bridged cation does not isomerize to the less stable U-type cation, it is not possible for the U-type product to be obtained in the reaction. The bridged bromonium cation transformed into the more stable N-type cation and the N-type product was obtained via this cation. The thermodynamic stability of the anti, exo and anti, endo isomers of N-type dibromide molecule were almost identical. N-type product is 11.759 kcal mol more stable than U-type product.

DFT Investigation of the Mechanism and Stereochemistry of Electrophilic Transannular Addition Reaction of Chlorine to Bisbenzotetracyclo[6.2.2.23,6 .02,7]tetradeca-4,9,11,13-tetraene.

The mechanism and stereochemistry of electrophilic addition of chlorine to bisbenzotetracyclo[6.2.2.23,6.02,7]tetradeca-4,9,11,13-tetraene (BBTT) molecule were investigated by DFT methods. The geometry and the electronic structure of BBTT molecule was studied by DFT/B3LYP method using the 6-311G(d) and 6-311++G(d,p) basis sets. The double bonds of BBTT molecule are endo-pyramidalized. The structure and stability of the cationic intermediates and products of the addition reaction were investigated by B3LYP/6-311G(d) and B3LYP/6-311+G(2d,p) methods. The solvent effect was evaluated using SCI-PCM method. The bridged chloronium cation is isomerized into the more stable nonclassical delocalized N- and U-type cations, and the difference between the stability of these cations is small. For the determination of the direction of addition reaction and the stereochemistry of the products, the stability of nonclassical delocalized N- and U-type ions and the structure of their cationic centres play a vital role for the determination of the direction of addition reaction and the stereochemistry of the products. Since the cationic centre of the N-type ion is in interaction with the benzene ring from the exo face, the nucleophilic attack of the chloride anion to this centre occurs from the endo face, and the exo,endo-isomer of the N-type product is obtained. The attack of chloride anion towards the cationic centre of U-type ion from the endo face is sterically hindered by the hydrogen atom, therefore the attack occurs from the exo face, which interacts with the benzene ring and the more stable exo,exo-isomer of U-type product is formed. Although, the U-type cation was 3.485 kcal mol-1 more stable than the N-type cation, the U-type product was 1.886 kcal mol-1 [SCI-PCM-B3LYP/6-311++G(2d,p)// B3LYP/6-311G(d)] less stable than the N-type product.

DFT and MP2 study on the electrophilic addition reaction of bromine to exo-tricyclo[3.2.1.0(2.4)]oct-6-ene.

The geometry and electronic structure of exo-tricyclo[3.2.1.0(2,4)]oct-6-ene (exo-TCO) was investigated using DFT methods. The two faces of the endo-pyramidalised double bond of the molecule are not equivalent. The exo face of the double bond has regions with high electron density (q (i,HOMO)) and greater negative potential. Molecular complexes of exo-TCO with bromine were investigated using the B3LYP/6-311++G(d,p) method; the exo-TCO . . . Br(2)(exo) molecular complex was found to be relatively more stable than the exo-TCO . . . Br(2)(endo) complex. The cationic intermediates of the reaction were studied by DFT and MP2 methods. The solvent effect was evaluated using the self-consistent isodensity polarised continuum model (SCI-PCM). The exo-bromonium cation was found to be more stable than the endo-bromonium cation. Exo-facial selectivity due to electronic and steric factors was observed upon addition of bromine to exo-TCO. The multicentre nonclassical delocalised bromocarbonium cation IV and the exo-bridged-bromonium cation I are more stable than the rearrangement cation V. The reaction products are formed via exo-bridged-bromonium I and nonclassical IV cations, which are the most stable intermediates and whose stabilities barely differ. The mechanism of the addition reaction is also discussed.

Density functional theory investigation of electrophilic addition reaction of bromine to tricyclo[4.2.2.2(2,5)]dodeca-1,5-diene.

The geometry and the electronic structure of tricyclo[4.2.2.2(2,5)]dodeca-1,5-diene (TCDD) molecule were investigated by DFT/B3LYP and /B3PW91 methods using the 6-311G(d,p) and 6-311++G(d,p) basis sets. The double bonds of TCDD molecule are syn-pyramidalized. The structure of pi-orbitals and their mutual interactions for TCDD molecule were investigated. Potential energy surface (PES) of the TCDD-Br(2) system was studied by B3LYP/6-311++G(d,p) method and the configurations [molecular charge-transfer (CT) complex, transition states (TS1 and TS2), intermediate (INT) and product (P)] corresponding to the stationary points (minima or saddle points) were determined. Initially, a molecular CT-complex forms between Br(2) and TCDD. With a barrier of 22.336 kcal mol(-1) the CT-complex can be activated to an intermediate (INT) with energy 15.154 kcal mol(-1) higher than that of the CT-complex. The intermediate (INT) then transforms easily (barrier 5.442 kcal mol(-1)) into the final, N-type product. The total bromination is slightly exothermic. Accompanying the breaking of Br-Br bond, C1-Br, C5-Br and C2-C6 bonds are formed, and C1 = C2 and C5 = C6 double bonds transform into single bonds. The direction of the reaction is determined by the direction of intramolecular skeletal rearrangement that is realized by the formation of C2-C6 bond.

Ab initio and DFT study of the inner mechanism and dynamic stereochemistry of electrophilic addition reaction of bromine to bisbenzotetracyclo[6.2.2.2(3,6).0 (2,7)]tetradeca-4,9,11,13-tetraene.

The inner mechanism and dynamic stereochemistry of electrophilic addition of bromine to bisbenzotetracyclo[6.2.2.2(3,6).0(2,7)]tetradeca-4,9,11,13-tetraene(BBTT) molecule have been investigated by the methods of quantum chemistry. The structure of the BBTT molecule has been studied by ab initio and DFT/B3LYP methods using the 6-31G(d) and 6-311G(d) basis sets. The double bonds of BBTT molecule are endo-pyramidalized. The structure and stability of the cationic intermediates and products of the addition reaction have been investigated by HF/6-311G(d), HF/6-311G(d,p), B3LYP/6-311G(d) and B3LYP/6-311++G(2d,p)//B3LYP/6-311G(d) methods. The bridged bromonium cation isomerized into the more stable nonclassical delocalized N- and U-type cations and the difference between the stability of these cations is small. For the determination of the direction of addition reaction and the stereochemistry of the products, the stability of nonclassical delocalized N- and U-type ions and the structure of their cationic centres play a vital role. Since the cationic centre of the N-type ion is in interaction with the benzene ring from the exo face, the nucleofilic attackof the bromide anion to this centre occurs from the endo face and the exo,endo-isomer of the N-type product is obtained. The attack of bromide anion, towards the cationic centre of U-type ion from the endo face is sterically hindered by the hydrogen atom therefore the attack occurs from the exo face, which interacts with the benzene ring and the more stable exo,exo-isomer of U-type product is formed. Although, the U-type cation was 2.232 kcal mol(-1) more stable than the N-type cation, the U-type product was 0.587 kcal mol(-1) less stable than the N-type product.

Ab initio and DFT investigation of electrophilic addition reaction of bromine to endo,endo-tetracyclo[4.2.1.1(3,6).0 (2,7)]dodeca-4,9-diene.

Full geometric optimization of endo,endo-tetracyclo[4.2.1.1(3,6).0(2,7)]dodeca-4,9-diene (TTDD) has been carried out by ab initio and DFT/B3LYP methods and the structure of the molecule investigated. The double bonds of TTDD molecule are endo pyramidalized. The structure of pi-orbitals and their mutual interactions for TTDD molecule were investigated. The cationic intermediates and products obtained as a result of the addition reaction have been studied using the HF/6-311G(d), HF/6-311G(d,p) and B3LYP/6-311G(d) methods. The bridged bromonium cation isomerized into the more stable N- and U-type cations and the difference between the stability of these cations is small. The N- and U-type reaction products are obtained as a result of the reaction, which takes place via the cations in question. The stability of exo, exo and exo, endo isomers of N-type product are nearly the same and the formation of both isomers is feasible. The U-type product basically formed from the exo, exo-isomer. Although the U-type cation was 0.68 kcal mol(-1) more stable than the N-type cation, the U-type product was 4.79 kcal mol(-1) less stable than the N-type product.

Ab initio and DFT study on the electrophilic addition reaction of bromine to tetracyclo[5.3.0.0(2,6).0 (3,10)]deca-4,8-diene.

The electronic and geometric structures of tetracyclo[5.3.0.0(2,6).0(3,10)]deca-4,8-diene (hypostrophene) have been investigated by ab initio and DFT/B3LYP methods using the 6-31G* and 6-311G* basis sets. The double bonds of hypostrophene are endo-pyramidalized. The cationic intermediates and products formed in the addition reaction have been investigated using the HF/6-311G*, HF/6-311G**, and B3LYP/6-311G* methods. The bridged bromonium cation was more stable than the U-type cation. Considering that the bridged cation does not isomerize to the less stable U-type cation, it is not possible for the U-type product to be obtained in the reaction. The bridged bromonium cation transformed into the more stable N-type cation and the N-type product was obtained via this cation. The thermodynamic stability of the exo, exo and exo, endo isomers of the N-type dibromide molecule were almost identical. The N-type product was 16.6 kcal mol(-1) more stable than the U-type product.

Ab initio and DFT study on the electrophilic addition of bromine to endo-tricyclo[3.2.1.0(2,4)]oct-6-ene.

Full geometric optimization of endo-tricyclo[3.2.1.0(2,4)]oct-6-ene (endo-TCO) by ab initio and DFT methods allowed us to investigate the structure of the molecule. The double bond is endo-pyramidalized and its two faces are no longer found to be equivalent. The exo face of the double bond has regions with far more electron density (q(i,HOMO)) and more negative electrostatic potential. The endo-TCO-Br2 system was investigated at the B3LYP/6-311+G** level and the endo-TCO...Br2(exo) molecular complex was found to be relatively more stable than the endo-TCO...Br2(endo) complex. The cationic intermediates of the reaction were studied by ab initio and DFT methods. The bridged exo-bromonium cation(I) is relatively more stable than the endo-bromonium cation(II). An absolute exo-facial selectivity should be observed in the addition reaction of Br2 to endo-TCO, which is caused by steric and electronic factors. The nonclassical rearranged cation IV was found to be the most stable ion among the cationic intermediates and the ionic addition occurs via the formation of this cation. The mechanism of the addition reaction is also discussed.

A molecular mechanics and semiempirical molecular orbital study on the conformation of polynorbornene chains.

The conformational analysis of polynorbornene (PNB) chains was investigated with the AM1, MM2, AMBER and OPLS methods taking into consideration the possibility of binding of norbornene monomers to each other at various positions, i.e. exo-exo, exo-endo, endo-endo. The chain that is formed by connecting exo-endo positions of the monomers has lower torsional barrier energy than those formed with bonds at other positions and has more flexibility. It is determined that the thredisyndiotactic chain formed by exo-endo addition adopts a helix structure and has a coil shape. The disyndiotactic chain formed by connecting norbornene monomers in mixed type has a linear structure. It is found that the repeat unit conformations of thredisyndiotactic and disyndiotactic chains of PNB are TGTG- and (TGTG-)2, respectively.