Novel [2 + 2] Photocycloaddition-Induced Rearrangement of Bichromophoric Naphthalene-Tethered Resorcinol Ethers

Hoffmann, Norbert; Pete, Jean‐Pierre; Inoue, Yoshihisa; Mori, Tadashi

doi:10.1021/jo011143m

Cited by 23 publications

(9 citation statements)

References 45 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Hoffmann and Pete and co-workers − later showed that phenol derivatives also give ortho adducts, which rearrange in situ under acidic catalysis into benzocyclobutane derivatives (Scheme ). Interestingly, the benzocyclobutanes were later exploited in thermal generation of orthoquinodimethane and subsequent trapping with a dienophile .…”

Section: Ortho Cycloadditionsupporting

confidence: 89%

Arene–Alkene Cycloaddition

2016

View full text Add to dashboard Cite

Cycloadditions are among the most efficient chemical processes, combining atom economy, stereospecificity, and the ability to generate molecular complexity in a single step. Aromatic rings would in principle be ideal reaction partners, as they contain, at least from the topological point of view, both olefinic and diene subunits; however, the stability of the conjugated aromatic system would be broken by cycloaddition reactions, which are therefore rarely applied, because kinetics and thermodynamics hinder the process. From that aspect, photochemical activation opens interesting perspectives, as one can selectively provide excess energy to one of the reactants but not to the product, thus preventing thermal back reaction. Indeed, aromatic rings show a rich photochemistry, ranging from isomerizations, substitutions, and additions to cycloadditions. In this review, we will focus on cycloadditions, covering literature from early observations up to the present.

show abstract

Section: Ortho Cycloadditionsupporting

confidence: 89%

Arene–Alkene Cycloaddition

2016

View full text Add to dashboard Cite

show abstract

“…When the reaction is carried out in an acidic medium, the tetrahydrofurane moiety of the primary cycloadducts 63a,b is protonated (Scheme 9). 65,66 Intermediates 64a,b rapidly rearrange and benzocyclobutenes (65a,b) Benzocyclobutenes obtained in this convenient way are valuable synthetic intermediates. 67 In the present case, some of them were transformed into nitrogen containing heterocycles, such as benzooctahydroisoquinolines 68.…”

Section: The [2 + 3] or Meta Photocycloadditionmentioning

confidence: 99%

“…Similar [2 + 2] photocycloadditions in an acidic medium have been carried out with resorcinol derivatives carrying a naphthyl group on the side chain (see below). 66 Acid catalysis is involved as well in more complex multi step rearrangements, as depicted for compounds 54 and 58 (Scheme 8). No photochemical reactivity was detected when the salicylic acid derivative 69 was irradiated in a neutral reaction medium.…”

Section: The [2 + 3] or Meta Photocycloadditionmentioning

confidence: 99%

Photochemical reactions of aromatic compounds and the concept of the photon as a traceless reagent

Hoffmann

2012

Photochem Photobiol Sci

Self Cite

124

View full text Add to dashboard Cite

Electronic excitation significantly changes the reactivity of chemical compounds. Compared to ground state reactions, photochemical reactions considerably enlarge the application spectrum of a particular functional group in organic synthesis. Multistep syntheses may be simplified and perspectives for target oriented synthesis (TOS) and diversity oriented synthesis (DOS) are developed. New compound families become available or may be obtained more easily. In contrast to common chemical reagents, photons don't generate side products resulting from the transformation of a chemical reagent. Therefore, they are considered as a traceless reagent. Consequently, photochemical reactions play a central role in the methodology of sustainable chemistry. This aspect has been recognized since the beginning of the 20th century. As with many other photochemical transformations, photochemical reactions of aromatic, benzene-like compounds illustrate well the advantages in this context. Photochemical cycloadditions of aromatic compounds have been investigated for a long time. Currently, they are applied in various fields of organic synthesis. They are also studied in supramolecular structures. The phenomena of reactivity and stereoselectivity are investigated. During recent years, photochemical electron transfer mediated reactions are particularly focused. Such transformations have likewise been performed with aromatic compounds. Reactivity and selectivity as well as application to organic synthesis are studied.

show abstract

“…9 An intramolecular [2 ϩ 2] photocycloaddition between the naphthalene and resorcinol moieties of 8, followed by an acid-catalyzed rearrangement resulted in formation of tricyclic tetrahydrofuran derivatives 9 (Scheme 3). 10, 11 The reaction was optimized by irradiation at 300 nm, which resulted in preferential excitation of the naphthalene moiety. High regioselectivity was obtained for the intramolecular [2 ϩ 2] photocycloaddition of 3-oxocyclohexene carboxylic acid derivatives using chiral tether groups.…”

Section: Photocycloadditionsmentioning

confidence: 99%

11 Organic photochemistry

Boyd¹,

Zopp²

2003

Annu. Rep. Prog. Chem., Sect. B

View full text Add to dashboard Cite

This review covers the literature during publication year 2002 concerning organic photochemistry. The general areas of photochemical applications in organic synthesis and mechanistic studies are both covered. This review is selective rather than comprehensive, due to the large volume of publications in this field. Biological photochemistry is not covered.Of particular note in 2002 is the development of a smart photochromic system which links bis-naphthopyrans through a bis-thiophene moiety. 1 The thiophene tether undergoes a time-dependent change during irradiation, with its electron-donating ability varying due to hybridization changes at the spirocyclic carbon. The development of orthogonal photocleavable protecting groups, with intramolecular or intermolecular discrimination, was described. 2 Chiral discrimination in excited-state proton transfer was demonstrated through an enhanced proton transfer rate from 5,8-dicyano-2-naphthol to enantiopure 2-butanol, compared to the racemic solvent. 3 Progress in photoinduced asymmetric induction for photocyclization and geometric isomerizations was reported. [4][5][6] The highest levels of asymmetric induction were achieved in zeolites in combination with ionic or neutral chiral auxiliaries.

show abstract

Novel [2 + 2] Photocycloaddition-Induced Rearrangement of Bichromophoric Naphthalene-Tethered Resorcinol Ethers

Cited by 23 publications

References 45 publications

Arene–Alkene Cycloaddition

Arene–Alkene Cycloaddition

Photochemical reactions of aromatic compounds and the concept of the photon as a traceless reagent

11 Organic photochemistry

Contact Info

Product

Resources

About