Photochemical cycloadditions of ethene and propene to benzene

Mirbach, Marlis F.; Mirbach, Manfred J.; Saus, A.

doi:10.1016/s0040-4039(01)92802-3

Cited by 19 publications

(11 citation statements)

References 10 publications

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“…The result of these considerations is that the predicted stabilization of the ortho and meta complexes is essentially identical, in agreement with experimental results. 12 From numerous examples in Table 2 it can be seen that a donor substituent on the benzene ring promotes meta addition at the positions 2 and 6, ortho to the substituent. The HOMO of the substituted benzene is derived from S and is increased in energy.…”

Section: B Theorymentioning

confidence: 99%

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The meta photocycloaddition of arenes to alkenes

Cornelisse¹

1993

Chem. Rev.

209

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Section: B Theorymentioning

confidence: 99%

“…Gilbert and co-workers123 have investigated derivatives of 5-phenylpent-l-ene with methyl groups at the a-, /3-, and 7-position (for numbering see Scheme 3). The a-and 7-isomers (Table 4, entries 12 and 18) undergo 2,6-as well as 1,3-addition.…”

Section: Regioselectivity Stereoselectivitymentioning

confidence: 99%

The meta photocycloaddition of arenes to alkenes

Cornelisse¹

1993

Chem. Rev.

209

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“…These reactions also have considerable synthetic potential (see refs and for comprehensive reviews), yet, to date, only very limited theoretical work along assumed reaction paths has been reported. In this paper we report a study of the model reaction of benzene and ethene . Our objective is to understand the topology of this S 1 potential energy surface and thus to determine the role of the various intermediate structures that have been postulated to rationalize experimental observations.…”

Section: Introductionmentioning

confidence: 99%

“…With many arene + olefin systems one or both of the 1,2- and 1,3-cycloadditions proceed with good yields, whereas the 1,4-addition is a less efficient process preferred only in a few special cases. In the case of the model system, ethene adds to benzene forming primarily the meta adduct (φ = 0.11, 50 bar, 12 mol/L ethene + 1 M benzene in dichloromethane), and other products (φ = 0.08) most of which are either the ortho product or its photoproducts . The quantum yield is measured relative to the benzene fluorescence.…”

Section: Introductionmentioning

confidence: 99%

Conical Intersection Pathways in the Photocycloaddition of Ethene and Benzene: A CASSCF Study with MMVB Dynamics

et al. 1996

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Pathways involving possible conical intersections and radicaloid intermediates on the potential energy surface for the photocycloaddition of ethene to benzene have been studied using CASSCF geometry optimization and MMVB simulation of conical intersection decay dynamics. This study is intended as a model for arene-alkene photochemistry. The formation of one C-C bond occurs without barrier to yield a low energy conical intersection. Whilst many of the previously postulated intermediates do exist, the reactivity is shown to be controlled by this single conical intersection that has the geometry of a distorted tetrahedron with 4 carbon centers at its vertices. Such a structure is similar to the one encountered in the sigmatropic migration of the methyl group in but-1-ene and of the allyl group in hexa-1,5-diene. The dynamics of the decay at this conical intersection, studied with MMVB, show that one may form either the ortho, meta, or para products. However, ground state relaxation valleys have been located for the meta and ortho products only. This is consistent with experiment in solution where ortho and meta products are formed with approximately equal quantum yields.

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“…The cycloaddition of propene to Si-excited benzene under a pressure of 15 bar leads to the endo-and exo-1,3 adducts 36 and 37 (eq 51). 85 Compared to ethylene (see 36 37 section VIIB) the addition of propene to benzene is rather a clean reaction. Except for a small amount of polymer, no side products were formed.…”

Section: B Propenementioning

confidence: 99%