Functionalization of the benzobicyclo[3.2.1] octadiene skeleton possessing one isolated double bond via photocatalytic oxygenation

Vuk, Dragana; Horváth, Ottó; Marinić, Željko; Škorić, Irena

doi:10.1016/j.molstruc.2015.11.036

Cited by 9 publications

(10 citation statements)

References 21 publications

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“…However, if the accessibility of the outer C=C bond became hindered by annulation of a benzene to the outer side of the furan ring, even the negatively charged catalyst could promote oxygenation at the inner positions [18]. The significant effects of the charge of these photocatalysts were also observed in the photocatalytic oxygenation of different phenyl derivatives of the same skeleton [19]. In that case the substituents on the phenyl ring could also influence the types of the end-products More interestingly, changes of the position and the type of the heteroatom in the derivatives similar to 1 resulted in considerably (sometimes strikingly) deviating reaction routes under the same experimental conditions [20].…”

Section: (P)mn IV -Omentioning

confidence: 99%

New Functionalized Polycycles Obtained by Photocatalytic Oxygenation Using Mn(III) Porphyrins in Basic Media

2019

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According to our earlier observations, the products of photocatalytic oxygenations of furan and thiophene derivatives of benzobicyclo[3.2.1]octadiene with anionic and cationic manganese(III) porphyrin at pH = 7 strongly depended on the type and position of the heteroatom in the aromatic ring, as well as the charge of the photocatalyst. Hence, a significant pH increase (to 10) in these systems offered a reasonable tool to affect the diversity and yields of the oxygenation products. They were quantitatively separated by TLC and identified with NMR analyses. The results clearly indicated that the increase of HO− concentration, in most cases, considerably changed the product yield, e.g., enhanced it to 70% for the hydroxy-furyl derivative. Accordingly, the selectivity of the oxygenation of the furan compound could be improved in this way. In the case of one thienyl compound, however, even an additional product appeared, while the yields of the products of the other thiophene derivative (with cationic catalyst) decreased to zero, suggesting the application of lower pH for preparative purposes. The pH effects indicate that oxygenation reactions in these systems involve more photochemically generated oxidative agents, e.g., •OH and (P)Mn(V)=O), the role of which is affected by the pH increase in various ways.

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Section: (P)mn IV -Omentioning

confidence: 99%

New Functionalized Polycycles Obtained by Photocatalytic Oxygenation Using Mn(III) Porphyrins in Basic Media

2019

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“…Tricyclic derivatives 2a-d have a benzobicyclo[3.2.1]butadiene skeleton containing an isolated double bond that can easily be further modified [5] into functionalized structural parts resulting in the total synthesis of biologically active compounds. In photochemical cycloaddition reactions they gave new tricyclic and tetracyclic derivatives with high stereoselectivity.…”

Section: Discussionmentioning

confidence: 99%

“…In photochemical cycloaddition reactions they gave new tricyclic and tetracyclic derivatives with high stereoselectivity. Tricyclic derivatives 2a-d have a benzobicyclo[3.2.1]butadiene skeleton containing an isolated double bond that can easily be further modified [5] into functionalized structural parts resulting in the total synthesis of biologically active compounds. Tetracyclic derivatives 3a and 3d contain a polycyclic skeleton that is almost impossible to synthesize in ground-state chemistry.…”

Section: New Butadiene Derivatives Ez-and Ee-3/4-[4-(2-vinyl-mentioning

confidence: 99%

“…[2] When properly functionalized, bicyclo[3.2.1]octanes have proved to be useful reactive intermediates in stereoselective transformations. [5] During our long-standing studies in photochemical intramolecular cycloaddition reactions of various -heteroaryl-o-divinylbenzenes such as furans, [6][7][8] thiophenes, [8][9][10] pyrroles, [11,12] sydnones, [13][14][15] and most recently oxazoles, [16][17][18] routes were obtained for a whole library of polycyclic compounds that include a vast number of structures with the benzobicyclo[3.2.1]octadiene moiety (A-D) (Scheme 1). [3,4] The benzobicyclo[3.2.1]octadiene skeleton can thus be even more useful, as it can easily be transformed by adding various functional groups to the isolated double bond.…”

Section: Introductionmentioning

confidence: 99%

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Formation of Polycyclic Skeletons by Photochemical Transformations of Pyridyl‐ and Thienylbutadiene Derivatives

et al. 2017

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In order to study the influence of heterocyclic nuclei on the photochemical behavior of conjugated butadiene systems, novel butadiene derivatives E,Z‐ and E,E‐2/3‐[4‐(2‐vinylphenyl)buta‐1,3‐dienyl]thiophene as well as E,Z‐ and E,E‐3/4‐[4‐(2‐vinylphenyl)buta‐1,3‐dienyl]pyridine have been synthesized. The Wittig reaction was utilized in a two‐step reaction course. During the first Wittig reaction, the corresponding aldehydes, namely 2/3‐thiophenecarboxaldehyde and 3/4‐pyridinecarboxaldehyde, reacted with formylmethylenetriphenylphosphorane to give the corresponding acrylaldehydes, which reacted with the diphosphonium salt of α,α′‐o‐xylenedibromide in the second Wittig reaction to give new butadiene derivatives. These butadiene derivatives afforded, by photochemical intramolecular cycloaddition, new fused tricyclic as well as tetracyclic derivatives. For the first time, a study of efficiency was conducted where the efficiency of intramolecular cycloaddition of these heterocyclic butadiene derivatives was investigated by simultaneous use of ferrioxalate and valerophenone actinometers.

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“…[21] Bicyclo[3.2.l]-skeleton can be constructed using different synthetic pathways, one of which is the photochemical cycloaddition approach that has been developed by our group in batch and flow photochemical reactor. [22][23][24][25][26][27][28][29][30][31][32][33][34] Guided by all above mentioned compounds, we have selected 32 compounds from both types of photoproducts and investigated their biological activity in proliferation and inflammation based assays. Effect of compounds on proliferation of several cancer cell lines was determined by measuring cell metabolic activity through time.…”

Section: Introductionmentioning

confidence: 99%

Antiinflammatory and Antiproliferative Activity of Naphthoxazole, Fused Hetero-benzoxazole and Bridged Benzobicyclic Photoproducts

Šagud

Ratković

Cedilak

et al. 2019

Croat. chem. acta (Online)

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Biological activity of naphthoxazoles, fused hetero-benzoxazoles and benzobicyclo[3.2.1]-derivatives was investigated in proliferation and inflammation based assays. The tested compounds were prepared by photocylization or photocycloaddition reactions. Effect of compounds on proliferation of several cancer cell lines was determined by measuring cell metabolic activity through time. Lipopolysaccharide (LPS) stimulation of peripheral blood mononuclear cells (PBMC) was used to investigate antiinflammatory properties of the compounds. Several naphthoxazoles and fused hetero-benzoxazoles inhibited TNFα protein expression in LPS stimulated PBMC, indicating possible antiinflammatory role which would be interesting to further investigate. Physico-chemical properties of tested compounds have been also studied using chromatographic lipophilicity measure, chrom logD and logP was calculated as the importance of physico-chemical properties of compounds at early stage of discovery of new drugs is well established. The similarities in structure and activity of some representative compounds affirm the need to further address their antiinflammatory properties.

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Functionalization of the benzobicyclo[3.2.1] octadiene skeleton possessing one isolated double bond via photocatalytic oxygenation

Cited by 9 publications

References 21 publications

New Functionalized Polycycles Obtained by Photocatalytic Oxygenation Using Mn(III) Porphyrins in Basic Media

New Functionalized Polycycles Obtained by Photocatalytic Oxygenation Using Mn(III) Porphyrins in Basic Media

Formation of Polycyclic Skeletons by Photochemical Transformations of Pyridyl‐ and Thienylbutadiene Derivatives

Antiinflammatory and Antiproliferative Activity of Naphthoxazole, Fused Hetero-benzoxazole and Bridged Benzobicyclic Photoproducts

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