Construction of new fluorophores by Diels-Alder reaction of diacenaphthothiophenes

Yamamoto, Yoshihiko; Fukuoka, Yoshiaki; Nishida, Jun‐ichi; Kitamura, Chitoshi; Kawase, Takeshi

doi:10.1016/j.tet.2017.08.016

Cited by 8 publications

(8 citation statements)

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“…DA reactions were performed by stirring separate o ‐xylene solutions of 3 b containing 6 a and 6 b at reflux for 4 d. These processes generated the respective 1:1 cycloadducts, DCMIs 2 a (17 %) and 2 b (13 %), as orange needles along with the 1:2 adducts, BMIAs 8 a (65 %) and 8 b (67 %), as pale‐yellow prisms. The pathway for the formation of the DCMIs involves [2+4] cycloaddition followed by desulfurization of resulting 1:1 adduct 10 and subsequent dehydrogenative aromatization of intermediate 11 (Scheme ) . In contrast, the BAIAs are generated by secondary DA reactions of intermediate 11 with 6 a and 6 b .…”

Section: Resultsmentioning

confidence: 99%

“…Absorption and emission spectroscopy studies were undertaken to gain information about the photophysical properties of the acceptor–donor–acceptor systems in 2 and 8 . The absorption spectra of model compounds 1 a , 2 a , and 5 b are shown in Figure , and the absorption and fluorescence spectra of 1:2 adducts 8 a and 9 a together with those of known benzyne bis‐adduct (BBA) 12 in CH 2 Cl 2 are shown in Figure . The absorption maxima ( λ ABS ), fluorescence maxima ( λ FL ), and fluorescence quantum yields ( Φ SN ) of these substances are listed in Table .…”

Section: Resultsmentioning

confidence: 99%

“…Shortly thereafter, Kilway and Peng's group reported the synthesis of tetra‐ tert ‐butyldecacyclene by using the DA reaction of 2,5,9,12‐tetra‐ tert ‐butyldiacenaphtheno[1,2‐ b ;1′,2′‐ d ]thiophene ( 3 b ) with acenaphthylene . This observation, which stands as the sole example of the preparation of a DC derivative having C 2 v symmetry, suggest that thiophene derivatives 3 a and 3 b should be versatile building blocks for the construction of polycyclic conjugated systems having potentially interesting electronic and optical properties …”

Section: Introductionmentioning

confidence: 98%

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Synthesis and Properties of a Decacyclene Monoimide and a Naphthalimide Derivative as Three‐Dimensional Acceptor–Donor–Acceptor Systems

Yamamoto

Yoshida

Morii

et al. 2018

Chemistry An Asian Journal

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A method involving the Diels-Alder (DA) cycloaddition of diacenaphtheno[1,2-b;1',2'-d]thiophenes (DATs) with N-alkylacenaphthylene-5,6-dicarboximides (AIs) was developed to synthesize decacyclene monoimides (DCMIs). The reactions generate the corresponding 1:2 adducts (BAIAs) as major products together with 1:1 adducts (the DCMIs). The molecular structure of BAIAb (N-octyl derivative) was unambiguously assigned as the bis-adduct having an endo,endo spatial disposition of the two acenaphthylene-5,6-dicarboximide moieties by using X-ray crystallographic analysis. Relative to the absorption spectrum of decacyclene triimide (DCTIa, N-2-ethylhexyl derivative), that of the analogous N-2-ethylhexyl-substituted monoadduct, DCMIa, is bathochromically shifted despite the fact that it possesses a less delocalized π-electron system. DCMIa does not fluoresce in various organic solvents, whereas DCTIa emits yellow fluorescence in CH Cl with a low quantum yield (Φ ). Moreover, DCMIa in CDCl displays concentration-dependent H NMR spectroscopy behavior, which suggests that it self-aggregates with an association constant (K ) of (193±50) m at 20 °C. Despite the presence of four bulky tert-butyl groups in DCMIa, its K value for aggregate formation is comparable to that of DCTIa [(495±42) m ], which does not contain tert-butyl substituents. Spectroscopic studies with the bis-adduct BAIAa (N-2-ethylhexyl derivative) show that it displays remarkable solvatofluorochromism corresponding to an emission maximum shift (Δλ ) of 100 nm. The results of density functional theory calculations on BAIAc (N-methyl derivative) demonstrate that a considerable spatial separation exists between the HOMO and LUMO coefficient distributions, which indicates that the ground-to-excited state transition of the novel three-dimensional acceptor-donor-acceptor BAIAa system should have intramolecular charge-transfer character.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 98%

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Synthesis and Properties of a Decacyclene Monoimide and a Naphthalimide Derivative as Three‐Dimensional Acceptor–Donor–Acceptor Systems

Yamamoto

Yoshida

Morii

et al. 2018

Chemistry An Asian Journal

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“…Thiophenes with pairs of fused polycyclic aromatic substituents, such as compound 4 (Fig. ), also perform well as dienes, reacting with dienophiles at the indicated C atoms . Reports employing 2‐vinylthiophenes as cycloaddition dienes are somewhat more common, but most examples used plain 2‐vinylthiophene.…”

Section: Introductionmentioning

confidence: 99%

A Diels–Alder/Ene Cascade Leading to 5‐(Pyrrolidin‐3‐yl)thieno[3,2‐e]isoindoles from Ketone‐derived 2‐Vinylthiophenes and N‐Phenylmaleimide

Noland

Huisenga

Herzig

et al. 2018

Journal of Heterocyclic Chem

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in Wiley Online Library (wileyonlinelibrary.com).In an extension of our prior work with indoles and pyrroles, the Diels-Alder chemistry of substituted 2vinylthiophenes was explored, using N-phenylmaleimide as the dienophile. The dienes were prepared from thiophene in two steps by addition to various ketones, followed by dehydration (40-60% overall yields). Although most dienes were obtained as regioisomeric mixtures, the Diels-Alder-derived products were easily purified by chromatography. The main cycloaddition pathway was endo Diels-Alder addition followed by exo ene addition of a second molecule of dienophile (19-33% yields). Several products were desulfurized with Raney nickel (48-62% yields). Unfortunately, no thiophene-derived products showed the promising biological activity of the previously reported indole analogs.

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“…chemistry with the similar diacenaphthothiophene based system. 18 For dimethyl acetylenedicarboxylate, the expected 1:1 adduct 4 was preferentially formed with an aromatic pi-sextet at the central cycloaddition position. The new aromatic unit limited further cycloaddition chemistry from proceeding.…”

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confidence: 99%

Diels-Alder Additions to 2,2’-Biaceanthrylene

Du¹,

Plunkett²

2021

Preprint

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A series of Diels-Alder reactions between the diene 2,2’-biaceanthylene and several dienophiles is presented. The diene is a cyclopenta-fused polycyclic aromatic hydrocarbon with anthracene units linked by two cyclopentene rings. Depending on the dienophile, the major product was the result of a single addition (dimethyl acetylenedicarboxylate) or double addition (quinone, benzyne) to the diene. Single crystal X-ray analysis of the quinone-derivative shows a propeller-like structure composed of mixed enantiomers. The synthesis and photophysical properties of these compounds is presented.<br>

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Construction of new fluorophores by Diels-Alder reaction of diacenaphthothiophenes

Cited by 8 publications

References 24 publications

Synthesis and Properties of a Decacyclene Monoimide and a Naphthalimide Derivative as Three‐Dimensional Acceptor–Donor–Acceptor Systems

Synthesis and Properties of a Decacyclene Monoimide and a Naphthalimide Derivative as Three‐Dimensional Acceptor–Donor–Acceptor Systems

A Diels–Alder/Ene Cascade Leading to 5‐(Pyrrolidin‐3‐yl)thieno[3,2‐e]isoindoles from Ketone‐derived 2‐Vinylthiophenes and N‐Phenylmaleimide

Diels-Alder Additions to 2,2’-Biaceanthrylene

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