Unique solvent effect on photochemistry of ortho-alkylphenacyl benzoates

Park, Bong Ser; Ryu, Hyuk Jun

doi:10.1016/j.tetlet.2010.01.046

Cited by 8 publications

(7 citation statements)

References 27 publications

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“…1−8 Moreover, owing to their use of noninvasive optical triggers, and its high spatial and temporal precision, photocaged substances have been utilized to explore biological processes and elucidate their mechanistic nature. 9−12 Arylcarbonylmethyl, 13 nitroaryl (ortho-nitrobenzyl, ortho-nitroanilides), 14 azobenzene, 15 xanthene, 16 coumarin-4-ylmethyl, 17−20 and indoline groups 21,22 are the commonly used photoreaction triggers to construct photocages for controlled release of metal ions (Ca 2+ , Zn 2+ , Cu 2+ ), drugs, and other bioactive substances. 23−27 Particularly, incorporation of nitrobenzene derivatives along with metal ion-binding ligands has become a prevailing tool to investigate the signaling processes in biological systems that are governed by metal ions.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Light promoted bond cleavage reactions of photocaged compounds serve as powerful tools to create materials in a highly spatially and temporally controlled manner. As a result, these substances have found wide applications in tissue engineering, biosensing, counterfeit detection, controlled release of functional molecules, and regulation of gene expression. − Moreover, owing to their use of noninvasive optical triggers, and its high spatial and temporal precision, photocaged substances have been utilized to explore biological processes and elucidate their mechanistic nature. − Arylcarbonylmethyl, nitroaryl ( ortho -nitrobenzyl, ortho -nitroanilides), azobenzene, xanthene, coumarin-4-ylmethyl, − and indoline groups , are the commonly used photoreaction triggers to construct photocages for controlled release of metal ions (Ca 2+ , Zn 2+ , Cu 2+ ), drugs, and other bioactive substances. − Particularly, incorporation of nitrobenzene derivatives along with metal ion-binding ligands has become a prevailing tool to investigate the signaling processes in biological systems that are governed by metal ions. − In addition, photocage containing metal ion complexes along with fluorophores whose optical properties are altered by metal ion binding and release have been employed to elucidate cellular processes and signaling …”

Section: Introductionmentioning

confidence: 99%

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Sanger’s Reagent Sensitized Photocleavage of Amide Bond for Constructing Photocages and Regulation of Biological Functions

Wei

Sun

et al. 2020

J. Am. Chem. Soc.

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Photolabile groups offer promising tools to study biological processes with high spatial and temporal control. In the investigation, we designed and prepared several new glycine amide derivatives of Sanger's reagent and demonstrated that they serve as a new class of photocages for Zn 2+ and an acetylcholinesterase (AChE) inhibitor. We showed that the mechanism for photocleavage of these substances involves initial light-driven cyclization between the 2,4dinitrophenyl and glycine methylene groups to form acyl benzimidazole N-oxides, which undergo secondary photoinduced decarboxylation in association with rupture of an amide bond. The cleavage reactions proceed with modest to high quantum yields. We demonstrated that these derivatives can be used in targeted intracellular delivery of Zn 2+ , fluorescent imaging by light-triggered Zn 2+ release, and regulation of biological processes including the enzymatic activity of carbonic anhydrase (CA), negative regulation of N-methyl-D-aspartate receptors (NMDARs), and pulse rate of cardiomyocytes. The successful proof-of-concept examples described above open a new avenue for using Sanger's reagentbased glycine amides as photocages for the exploration of complex cellular functions and signaling pathways.

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Section: ■ Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Sanger’s Reagent Sensitized Photocleavage of Amide Bond for Constructing Photocages and Regulation of Biological Functions

Wei

Sun

et al. 2020

J. Am. Chem. Soc.

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“…In general, the indanone 54 ( 5 ) and benzocyclobutenol 55 ( 6 ) side-products are formed in non-nucleophilic solvents, whereas acetophenone derivatives substituted on the o -methyl group 7 are produced in the presence of a nucleophile, such as methanol.…”

Section: Arylcarbonylmethyl Groupsmentioning

confidence: 99%

“…66 Klán and co-workers showed that photolysis of 4,5-dimethoxy-2-methylphenacyl benzoate can lead to the corresponding indanone derivative that is a precursor for the subsequent synthesis of donepezil, a centrally acting reversible acetylcholinesterase inhibitor used to treat Alzheimer’s disease. 67 Park and collaborators have recently shown that photolysis of 2,4,6-trialkylphenacyl benzoates can also lead to the corresponding benzocyclobutenols ( 6 in Scheme 5) in addition to indanones, 55 whereas irradiation of α-dichloro-2-acetophenone yields a mixture of various photoproducts. 68 Berkessel and co-workers used the photoenolization reaction as a tool to study the cyclization of 4′-benzophenone-substituted nucleoside derivatives as models for ribonucleotide reductases.…”

Section: Arylcarbonylmethyl Groupsmentioning

confidence: 99%

Photoremovable Protecting Groups in Chemistry and Biology: Reaction Mechanisms and Efficacy

et al. 2012

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“…The compounds 10 and 13b , in which the photo-Favorskii pathway was suppressed by replacing the hydroxy with an alkoxy group, also followed the photoenolization pathway. Cyclobutanol 23 along with indanone 22 were formed from 13b in dry or aqueous acetonitrile, apparently via photoenol 25 (Scheme 4) similar to the cyclobutanols produced from 2,4,6-trialkylphenacyl benzoates 9…”

Section: Anhydrous Media: the Photoenolization Pathwaymentioning

confidence: 97%

The Power of Solvent in Altering the Course of Photorearrangements

et al. 2011

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A clean bifurcation between two important photochemical reactions through competition of a triplet state Type II H-abstraction reaction with a photo-Favorskii rearrangement for (o/p)-hydroxy-o-methylphenacyl esters that depends on the water content of the solvent has been established. The switch from the anhydrous Type II pathway that yields indanones to the aqueousdependent pathway producing benzofuranones occurs abruptly at low water concentrations (~8%). The surprisingly clean yields suggest that such reactions are synthetically promising.An intramolecular Type II reaction of alkylphenones, especially 2-methylacetophenoes, produces high yields of photoenols that have been shown to be valuable reactive intermediates. 1 When a leaving group (X) is present in the α-position of 2-alkylacetophenones (1), longer-lived (E)-photoenols liberate HX to give indanones 2 (2 ; Scheme 1) that can be employed as precursors to elaborate products used in synthetic methodology. 3 Likewise, the photo-Favorskii rearrangement of α-substituted phydroxyacetophenones (3) to p-hydroxyphenylacetic acid (4), discovered more recently, has enjoyed success in a variety of applications because of its rapid release of nucleofuges (Scheme 1). 4 Both reactions have exhibited very good photochemical efficiencies and are relatively free of side reactions that produce complicated product mixtures. The similarity of the chromophores, the common triplet state origin for reaction, and the extensive understanding of the mechanistic photochemistry 5 have prompted us to explore the intersection of the photochemical pathways to uncover which parameters control the pathway followed by a chromophore common to both. It is a rare occurrence in organic photochemistry when one can completely and cleanly divert the reaction or rearrangement pathway from a single product type to an alternative * parkbs@dongguk.edu; givensr@ku.edu; klan@sci.muni.cz. Supporting Information Available:Experimental details and characterization data for products are provided. This material is available free of charge via the Internet at http://pubs.acs.org. 3a Since it is well known that electron donating hydroxy and methoxy groups suppress Type II reactivity 6 and nearly as well known that the photo-Favorskii rearrangement has a strong affinity for water, 4k,7 we assumed that these two reaction pathways might be separated by the water content of the solvent media. In this work, the analogs of 4-hydroxyphenacyl derivatives with good leaving groups necessary for the photo-Favorskii process were fitted with 2-methyl substituent for efficient Type II hydrogen abstraction reaction to compete with the photo-Favorskii rearrangement. As an extension, a similar design, in which the 2-hydroxyphenacyl derivatives were fitted with a 6-methyl group, was also examined. NIH Public Access Synthesis of Phenacyl Esters4-Hydroxy-2-methyl (9a-c) and 2-hydroxy-4,6-dimethylphenacyl (14) esters, and the corresponding benzyl (10) and methyl (13) ethers were prepared by α-bromination of acetophen...

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Unique solvent effect on photochemistry of ortho-alkylphenacyl benzoates

Cited by 8 publications

References 27 publications

Sanger’s Reagent Sensitized Photocleavage of Amide Bond for Constructing Photocages and Regulation of Biological Functions

Sanger’s Reagent Sensitized Photocleavage of Amide Bond for Constructing Photocages and Regulation of Biological Functions

Photoremovable Protecting Groups in Chemistry and Biology: Reaction Mechanisms and Efficacy

The Power of Solvent in Altering the Course of Photorearrangements

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