Photo‐Diels‐Alder Reactions of Anthracene

Kaupp, Gerd; Dyllick‐Brenzinger, Rainer; Zimmermann, Ingfried

doi:10.1002/anie.197504911

Cited by 18 publications

(3 citation statements)

References 10 publications

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“…The conical intersection structure shown in Figure is included because this type of interaction may be important in the addition of dienes to aromatic systems, − in which the necessary distortions may be better accommodated by the σ framework than in butadiene. Scheme a,b show that the products of diene + aromatic photodimerization reflect the initial equilibrium of trans:cis isomers in the diene ground state, which for butadiene is ∼96:4. 20b,11c Although crossings C and E have been found to occur at trans + cis geometries ( C ct and E ct Figure ) it may be that the Figure crossing becomes competitive, as the radical centers can be efficiently delocalized.…”

Section: Resultsmentioning

confidence: 99%

“…Products have been characterized, and the formation of strained trans -diene adducts taken to indicate that the reaction is concerted. 17a,f (The product structure reflects the dominant ground state conformer of the diene, ,11c not the most stable product). The nature of any intermediates such as excimers is unclear,14f as product formation might account for deactivation 18a…”

Section: Introductionmentioning

confidence: 99%

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Modeling Photochemical [4 + 4] Cycloadditions: Conical Intersections Located with CASSCF for Butadiene + Butadiene

et al. 1997

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The [4 + 4] photocycloaddition of butadiene + butadiene has been studied at the CASSCF /4-31G level, as a prototype for a class of photochromic systems. For this model system, minima and transition structures are characterized by analytic frequency calculations, and conical intersections are located. Our results indicate that the standard model for the [4 + 4] addition (based on H4) needs to be revised. The reorganization of all 8π electrons is crucial (i.e., it is not always the same 4π electrons that are important). Efficient nonradiative decay of butadiene + butadiene can be explained by the presence of two distinct S 1/S 0 conical intersections. The first-the lowest-energy point on S 1 overall-is preceded by a barrier for the formation of a new σ bond. The resulting structure is similar to those previously characterized for methyl migration in but-1-ene and the addition of ethylene to benzene. A higher-energy barrier leads to a second crossing which resembles the rhomboidal funnel for the [2 + 2] addition of ethylene + ethylene, but which involves only one double bond from each butadiene. Both reaction paths commence at a true pericyclic minimum, at which the (S 0−S 1) energy gap of ∼37 kcal mol-1 prohibits decay.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Modeling Photochemical [4 + 4] Cycloadditions: Conical Intersections Located with CASSCF for Butadiene + Butadiene

et al. 1997

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“…The VG, however, may change little in the temperature range examined.30 Accordingly, calculations were made for Pj and a upon setting an arbitrary value for VG (see Appendix I) to reveal that temperature was quite insensitive to both parameters (see Table III for P, and a when VJVG = 10, where V0 is a total volume of the micellar solution), and perhaps this could also be so for POH and PdT. Though the calculations depend on the unconfirmed assumption of VG, these results accord with the small effect of temperature generally observed on partition coefficients in multiliquid phase systems.31 Thus, Kx may parallel closely Kx in the temperature characteristics (see eq 7). Figure 9 displays the plot of log Kx vs. T1 (K), giving fairly good straight lines.…”

Section: Discussionmentioning

confidence: 57%

Three-phase model of micellar reactions. Methylation of thymidine by (long-chain-alkyl)dimethylsulfonium iodides

Yamauchi¹,

Hisanaga²,

Kinoshita³

1983

J. Am. Chem. Soc.

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Supramolecular Photocatalysis by Utilizing the Host–Guest Charge‐Transfer Interaction: Visible‐Light‐Induced Generation of Triplet Anthracenes for [4+2] Cycloaddition Reactions

et al. 2020

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Supramolecular photocatalysis via charge‐transfer excitation of a host–guest complex was developed by use of the macrocyclic boronic ester [2+2]BTH‐F containing highly electron‐deficient difluorobenzothiadiazole moieties. In the presence of a catalytic amount of [2+2]BTH‐F, the triplet excited state of anthracene was generated from the charge‐transfer excited state of anthracene@[2+2]BTH‐F by visible‐light irradiation, and cycloaddition of the excited anthracene with several dienes and alkenes proceeded in a [4+2] manner in high yields.

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Photo‐Diels‐Alder Reactions of Anthracene

Cited by 18 publications

References 10 publications

Modeling Photochemical [4 + 4] Cycloadditions: Conical Intersections Located with CASSCF for Butadiene + Butadiene

Modeling Photochemical [4 + 4] Cycloadditions: Conical Intersections Located with CASSCF for Butadiene + Butadiene

Three-phase model of micellar reactions. Methylation of thymidine by (long-chain-alkyl)dimethylsulfonium iodides

Supramolecular Photocatalysis by Utilizing the Host–Guest Charge‐Transfer Interaction: Visible‐Light‐Induced Generation of Triplet Anthracenes for [4+2] Cycloaddition Reactions

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