Photoadditions of aromatic compounds

McCullough, John J.

doi:10.1021/cr00080a008

Cited by 185 publications

(64 citation statements)

References 176 publications

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“…The shortage of olefinic resonances suggests the presence of an additional (cyclopropane) ring; the assigned structure identifies it as a meta-cycloadduct, a product type often formed between an aromatic singlet state and alkenes, and formulated via exciplex intermediates. 24 Metacycloadducts may be formed as major products from aggregates with limited charge-transfer character; the present system clearly has considerable charge-transfer character, compatible with the formation of 8 and its isomers as minor products. The predominant products formed from CNN and N are [2 2]-cycloaddition products (4-7), suggesting exciplex formation as the key mechanism.…”

Section: Discussionmentioning

confidence: 57%

Stereospecific nucleophilic trapping of encounter complexes between photoexcited 1-cyanonaphthalene and norbornadiene

Weng

Roth

1998

J. Phys. Org. Chem.

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Photo-induced electron donor-acceptor reactions between 1-cyanonaphthalene (CNN) and norbornadiene (N) generate products of several structure types. Methanol adducts (1-3) formed in polar solvents are rationalized via the radical cation, N Á , and stereospecific (exo-) nucleophilic attack by methanol. In less polar solvents, CNN and N form [2 + 2]-cycloadducts, exclusively on the exo-face of N. In non-polar solvents containing methanol, CNN, N and methanol combine to form 1:1:1 adducts, containing the sensitizer on the endo-and the methoxy groups on the exo-face. The formation of these products is rationalized via the trapping of encounter complexes of different geometries. Any rearrangement of the norbornenyl system can be eliminated, since neither tricyclyl nor 7-methoxynorbornenyl structures are formed. Apparently, the alcohol captures an endo-encounter complex of CNN and N by attack from the exo-face, similar to the attack of methanol on N Á .

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Section: Discussionmentioning

confidence: 57%

Stereospecific nucleophilic trapping of encounter complexes between photoexcited 1-cyanonaphthalene and norbornadiene

Weng

Roth

1998

J. Phys. Org. Chem.

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“…Cycloaddition reactions that involve arenes encompass an important group of dearomatization strategies 23 . Aromatic compounds, known for their stability in the ground state, become exceptionally reactive upon photoexcitation and can undergo cycloaddition with a variety of alkenes 15 .…”

Section: Resultsmentioning

confidence: 99%

Dearomative dihydroxylation with arenophiles

et al. 2016

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Aromatic hydrocarbons are some of the most elementary feedstock chemicals, produced annually on a million metric ton scale, and are used in the production of polymers, paints, agrochemicals and pharmaceuticals. Dearomatization reactions convert simple, readily available arenes into more complex molecules with broader potential utility, however, despite substantial progress and achievements in this field, there are relatively few methods for the dearomatization of simple arenes that also selectively introduce functionality. Here we describe a new dearomatization process that involves visible-light activation of small heteroatom-containing organic molecules—arenophiles—that results in their para-cycloaddition with a variety of aromatic compounds. The approach uses N–N-arenophiles to enable dearomative dihydroxylation and diaminodihydroxylation of simple arenes. This strategy provides direct and selective access to highly functionalized cyclohexenes and cyclohexadienes and is orthogonal to existing chemical and biological dearomatization processes. Finally, we demonstrate the synthetic utility of this strategy with the concise synthesis of several biologically active compounds and natural products.

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“…Our previous finding that 1-naphthonitrile (5), when excited in the presence of 2, does not give rise to any 1,4-adduct, instead the two cyclobutanaphthalenes 6 and 7 were formed, 12 is in analogy to related cases in the literature 10,11 (Scheme 2). …”

Section: Methodsmentioning

confidence: 70%

Photocycloaddition of four homologous 2-(cycloamino)propenenitriles to 1-acetonaphthone

Döpp¹,

Kruse²,

Erian³

et al. 2013

Arkivoc

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2-(Cycloamino)propenenitriles H 2 C=C(CN)N(CH 2 ) n (n = 4, 5, 6, 7) are added to triplet π,π*-excited 1-acetonaphthone forming 8b-acetyl-2-(cycloamino)-1,2,2a,8b-tetrahydrocyclobuta-[a]naphthalene-2-carbonitriles as well as 1-acetyl-9-(cycloamino)-1,4-dihydro-1,4-ethanonaphthalene-9-carbonitriles. Regio-and stereoselectivity of the photocycloadditions and the special role of the cyclobuta[a]naphthalene adducts in the initial stage of the photoadditions are discussed.

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Photoadditions of aromatic compounds

Cited by 185 publications

References 176 publications

Stereospecific nucleophilic trapping of encounter complexes between photoexcited 1-cyanonaphthalene and norbornadiene

Stereospecific nucleophilic trapping of encounter complexes between photoexcited 1-cyanonaphthalene and norbornadiene

Dearomative dihydroxylation with arenophiles

Photocycloaddition of four homologous 2-(cycloamino)propenenitriles to 1-acetonaphthone

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