Photocycloaddition of Aromatic Compounds

Due to their reduced aromatic character, naphthalene derivatives more easily undergo [2 + 2] photocydoaddition to give access to cyclobutane derivatives [49]. In some cases, the formal [4 + 2] addition is competitive. In contrast to the ground-state Diels-Alder reaction, the [4 + 2] products from these photochemical reactions result from a multistep reaction. Upon irradiation, the 1-cyanonaphthalene derivative 45 

Depending on the substitution pattern in naphthalene derivatives, the solvent polarity, and particularly also the irradiation time, the formation of the meta adducts can be increased [50]. 

Frequently, the intramolecular [2 + 2] photocydoaddition of an alkene to a benzene ring is followed by further pericyclic reactions. Such transformations yield 

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Scheme 5.11 Synthesis of tricyclic cyclo butene derivatives with intramolecular [2 + 2] photocycloadditions of aromatic compounds. The addition is followed by rearrangements leading to the final products.

The simultaneous formation of two or more a-bonds has always attracted synthetic chemists since complex molecules can be built up in one single step. Therefore it is not surprising that highly developed syntheses of natural and artificial products often made use of cycloaddition procedures. The meta photocycloaddition of aromatic compounds to alkenes certainly belongs to this category and has reached its summit of application in the admirable work of Wender s group. Hence this chapter describes photocycloadditions of various types covering mainly meta [3+2], ortho [2+2] and para [4+2] ones. Even an unusual example of an [6+6] cycloaddition is presented. The fact that only one substitution reaction is described may indicate that synthetic studies of electron transfer activation only started recently. 

Among the photochemical reactions of aromatic compounds, the photocycloadditions are most frequently applied to the synthesis of complex polycyclic compounds [6, 9]. The [2+3] or meta photocycloaddition of aromatic compounds and alkenes is the most prominent example [10]. This transformation also demonstrates complementarities between photochemical and ground state reactions since such reactions are almost impossible using conventional activation. A [2+2] ot ortho photocycloaddition between carbocyclic aromatic compounds and alkenes is observed as well. It is often competitive with other cycloaddition modes, in particular the [2+3] mode [11]. Many of these reactions are reversible, and photostationary equilibria are involved. This reaction was much less applied to organic synthesis. Recently, it was found that an acidic reaction medium may have an influence on the outeome of the reaction. The intramolecular photocycloaddition of resorcinol derivatives such as 1 is difficult due to its reversibility (Scheme 29.1). However, in an acidic reaction medium, the cycloadducts 2a,b are protonated at the oxygen atom of the tetrahydrofuran moiety... 

Synthetic applications of these photocycloadditions to aromatic compounds are sometimes hampered by low chemical yields and poor selectivity in the photoreactions. However, a number of elegant syntheses of tricyclic sesquiterpenes have been hased on intramolecular 1,3-phutocycloadditions ie.g. 3. SI), and these represent a completely new approach to the preparation of such systems. 

A. Gilhert, in W. M. Horspocl (ed.). Synthetic Organic Photochemistry, Plenum 11984). Photoaddition, photocycloaddition and photocyclization processes of aromatic compounds are all covered in this account of synthetic aspects of aromatic photochemistry. 

This chapter deals primarily with the intermolecular and intramolecular photocycloaddition of unsaturated compounds to aromatic rings and the inter-... 

Whether the role of the second olefinic partner is catalytic or a triplex intermediate is involved is not yet clear. The role of triplexes in photoreactions of aromatic compounds with olefins may be even more complex. For example, excited biphenyl forms both a fluorescent dual and triple exciplex with 2,3-dimethyl-2-butene [120]. The possibility of these two pathways of deactivation can explain the inefficient photocycloaddition in the particular case of 1biphenyl /cyclopentene [121]. 

A variety of four-membered ring compounds can be obtained with photochemical reactions of aromatic compounds, mainly with the [2 + 2] (ortho) photocycloaddition of alkenes. In the case of aromatic compounds of the benzene type, this reaction is often in competition with the [3 + 2] (meta) cycloaddition, and less frequently with the [4 + 2] (para) cycloaddition (Scheme 5.7) [38-40]. When the aromatic reaction partner is electronically excited, both reactions can occur at the 7t7t singlet state, but only the [2 + 2] addition can also proceed at the %% triplet state. Such competition was also discussed in the context of redox potentials of the reaction partners [17]. Most frequently, it is the electron-active substituents on the aromatic partner and the alkene which direct the reactivity. The [2 + 2] photocycloaddition is strongly favored when electron-withdrawing substituents are present in the substrates. In such a reaction, crotononitrile 34 was added to anisole 33 (Scheme 5.8, reaction 15) [41 ], and only one regioisomer (35) was obtained in good yield. In this transformation, the... 

The most characteristic photochemical reaction of aromatic compounds is their cydoaddition with alkenes. The intramolecular reaction is suitable for the synthesis of complex structures, such as those depicted in Scheme 9.49, where [3+2]-photocycloaddition leads to structures which resemble natural products (aphidico-line and stemoclinone). An interaction of the arene singlet excited state with the alkene ground state gives rise to the meta adduct [83, 84]. 

Mizuno K, Maeda H, Sugimoto A, Chiyonobu K. Photocycloaddition and photoaddition reactions of aromatic compounds. In Ramamurthy V, Schanze KS, eds. Molecular and Supramolecular Photochemistry. Vol 8. New York Marcel Dekker, Inc., 2001 127-316. 

Intramolecular Cyclization Reactions This Section is concerned with photo-induced cyclization reactions of aromatic compounds in which the final product is also an arene. Examples of intramolecular cyclization in which the product is a stable aliphatic system (e.g. intramolecular meta photocycloaddition of ethylenes to benzenes) are considered in Section 3 of this Chapter. The present type of process occurs for a wide variety of systems and may involve arene-arene and arene-ethylene photo-oxidative cyclization or reactions proceeding by loss of halogen acid. For several years now one of the major interests in these processes has been in their use as synthetic procedures and again within the review period there have appeared a number of accounts which illustrate this feature. Stilbene-... 

Comeliesse, J., de Haan, R., Ortho Photocycloaddition Reactions of Aromatic Compounds. In Ramamurthy, V., Schanze, K. (eds), Understanding and Manipulating Excited state Processes, Marcel Dekker, New York, 2001, pp. 1 126. 

Several reviews have been published within the year which are of general relevance to the photoreactions of aromatic compounds. The subjects of these reviews include photochemistry in ionic liquids and in isotropic and anisotropic media, organic synthesis utilizing photoinduced electron-transfer reactions," heteroatom-directed photoarylation processes, photochromism, and photochemical molecular devices. Reviews more directly pertinent to the sections in the present chapter include those of the photoisomerization of five-membered heteroaromatic azoles, the photocycloaddition of benzene derivatives to alkenes, Diels-Alder additions of anthracenes, advances in the synthesis of polycyclic aromatic compounds, diarylethene-based photochromic switches, the photo-Fries rearrangement, and the application of Diels-Alder trapping of photogenerated o-xylenols to the synthesis of novel compounds. " A number of chapters in the two recently published handbooks of photochemistry and photobiology and in the revised edition of the text on photochromism are also pertinent to the current subject matter. 

A lot of photochemical reactions of aromatic compounds have been described in the literature. In this context, photocycloadditions are typical examples [6, 9]. In such reactions involving nn excitation of the chromophore, the aromatic character is not reestablished in the final products as is typical for ground state reactions. Very efficient methods based on this reactivity have been developed for the construction of polycyclic compounds. Thus, molecular complexity is generated from simple and easily available starting compounds in only one step. For these reasons, photochemical... 

Photocycloaddition Reactions of Aromatic Compounds with Unsaturated Compounds... 

The photochemical cycloadditions of alkenes and alkynes with aromatic compounds have received by far the most attention. Yields of [2+2] cydoadducts can be good, but reaction times are often long and secondary rearrangement products are common [139, 140, 141,142, 143,144, 145,146] (equations 63-65). The pioneering mechanistic and synthetic work on aromatic photocycloadditions has been reviewed [147],... 

Aromatic compounds can participate in both [2+2] and [4+2] photocycloaddition reactions with uracil derivatives to give either benzocyclobutane or ethenoquinazoline (barrelene) derivatives, which can then undergo a number of subsequent photochemical reactions. The products obtained are dependent upon the reaction conditions, and thus the photocycloaddition reaction between naphthalenes 470 and l,3-dimethyl-5-fluorouracil 471 in cyclohexane gave 4a-fluoro-5,10-ethenobenzo[/]quinazolines 472 as products as a result of a [4+2] photocycloaddition (photo-Diels-Alder) reaction <2002TL3113, 2003H(61)377>. 

Photocycloadditions of naphthalene derivatives to alkcnes have been recently reviewed.60 Examples of such reactions are the photocycloaddition of naphthalene to 2,3-dihy-drofuran,61 of 4-methoxy-l-naphthonitrile to acrylonitrile62 and of 2-trimethylsiloxynaph-thalene to methyl acrylate.63 2-Naphthols undergo cycloaddition with ethene in the presence of aluminum trihalides only.64 Other bicyclic aromatic compounds, e.g. A-acylindoles65-67 and /V-methylphenanthrene-9,10-dicarboximide,68 have also been studied in detail. Irradiation of 5/f-dibenzo[u,i7]cyclohepten-5-one (21) and dimethyl 2-methylfumarate (22) in dioxane gives the cyclobutane adduct 23 in 73% yield.69... 

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