Discovery of Deep-Seated Skeletal Rearrangements in the Photocyclizations of Some <i>tert</i>-Butyl-Substituted 1,2-Diarylethylenes

Mallory, Frank B.; Regan, Colleen K.; Bohen, Joseph M.; Mallory, Clelia W.; Bohen, Alyssa; Carroll, Patrick J.

doi:10.1021/jo501965y

Cited by 16 publications

(9 citation statements)

References 14 publications

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“…The reaction undergoes condensation and Mallory type photocyclization in absence of I 2 at room temperature by the use of simple 40 W yellow light bulb. Initially, we tried benzene, one of the most preferred solvent for Mallory oxidative photocyclization, 21,22 which resulted a low yield (<35% crude). After optimization, ethyl acetate was found better to achieve 65% crude yield.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of multi ring-fused imidazo [1,2-a]isoquinoline-based fluorescent scaffold as anti-Herpetic agent

Chakravarty

Ojha

Konreddy

et al. 2015

Antivir Chem Chemother

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Background: Natural product-inspired synthesis is a key incorporation in modern diversity-oriented synthesis to yield biologically novel scaffold. Inspired by b-carboline fused system, we have designed molecules with multi ring fused scaffold by modifying the tricyclic pyrido [3,4-b]indole ring with imidazo[1,2-a]isoquinoline. Methods: A highly convergent approach with new C-N and C-C bond formation to synthesize multiring fused complex scaffold imidazo[1,2-a]isoquinolinies as fluorophores. N-nucleophile-induced ring transformation of 2H-pyran-2-one followed by in situ cis-stilbene-type oxidative photocyclization yielded new C-C bond formation without additional oxidant. The cytotoxicity, effective concentrations, and the mode of action of the synthesized analogs were determined by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT),, plaque reduction, time of addition, and reverse transcriptase Polymerase Chain Reaction (PCR). Results: Novel imidazo[1,2-a]isoquinoline analogs were prepared, and the results revealed that trans isomer of cyclopropyl analog (EC 50 35 and 37.5 mg/ml) and trans isomer of citric acid salt of phenyl analog (EC 50 38.2 and 39.8 mg/ml) possess significant anti-Herpes Simplex Virus (HSV) activity with selectivity index of >10. The kinetic study demonstrated that both the analogs inhibited HSV-1F and HSV-2G at 2-4 h postinfection. Finally, western blot and reverse transcriptase PCR assays revealed that both the analogs suppressed viral immediate early transcription. Conclusion: Novel imidazo[1,2-a]isoquinoline analogs were synthesized from pyranone with appropriate amines. Two compounds showed better antiviral profile on HSV-infected Vero cells, compared to the standard drug acyclovir (ACV). Overall, we discovered a promising scaffold to develop a nonnucleoside lead targeting the viral immediate early transcription for the management of HSV infections.

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Section: Resultsmentioning

confidence: 99%

Synthesis of multi ring-fused imidazo [1,2-a]isoquinoline-based fluorescent scaffold as anti-Herpetic agent

Chakravarty

Ojha

Konreddy

et al. 2015

Antivir Chem Chemother

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“…The relative intensities of the absorption bands are indicated as vs = very strong (>90%), s = strong (70−90%), m = medium (40− 70%), and w = weak (<40%). 1 H-NMR and 13 C-NMR spectra were recorded on a Bruker Avance III HD, 400 MHz/ probehead 5 mm PBBO; δ in ppm, J in Hz. Chemical shifts are given in ppm relative to internal tetramethylsilane (TMS), while coupling constants are reported in hertz (Hz).…”

Section: Methodsmentioning

confidence: 99%

“…Iron-catalyzed bromination of neat 11 proceeded very smoothly resulting in a high degree of monobrominated product (70%). 13 Iodine-catalyzed bromination was also found to give reasonable regioselectivity toward 13, but it resulted in some formation of dihalogenated product. To avoid the gaseous byproducts, the halogenation can be carried out using N-bromosuccinimide (NBS) 14 or under the conditions of Iskra et al, generating the halogenating reagent in situ from a halide salt under oxidative conditions.…”

Section: -Phenyl Propanal By the Heck Reactionmentioning

confidence: 99%

Process Research and Scale-Up Synthesis of 3-(4-Isobutyl-2-methylphenyl)propanal, a Safe and Uniquely Performing Perfumery Ingredient

Lovchik

Tse

Ellwood

2020

Org. Process Res. Dev.

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Ever since the beginning of modern perfumery, muguet (lily-of-the-valley) notes have been sought after and are now found in varying doses in practically every perfume composition, accounting for the warm, soft, and comforting facets of many fragrances. Over the past decades, Lilial and Bourgeonal have evolved to become popular and inexpensive ingredients to satisfy the high demand of such floral odors. However, the search continues for more performing ingredients, especially in this odor family. Through this effort, 3-(4-isobutyl-2-methylphenyl)propanal (Nympheal) was identified as a modern, more performing, and benign alternative to the traditional ingredients. In particular, it outperforms Lilial in a sense that it has a linden blossom, a floral aldehydic odor considered to be more natural in its character. This paper details the challenge to design an efficient synthesis for the multi-kilogram production of the fragrance ingredient Nympheal. The methyl group, strategically placed in the 2-position to ensure the biological safety of the ingredient, also introduced a level of asymmetry into the molecule resulting in regiochemical challenges to identifying potential synthetic routes. Route scouting for this initial scale-up was performed using 1-isobutyl-3-methylbenzene as a feedstock made by continuous dehydrogenation of a mixture of 3- and 5-isobutyl-1-methylcyclohex-1-ene. Different routes were explored for introduction of the propanal moiety including carbonylation, Heck reaction, and Friedel–Crafts reaction. Ultimately, 3.3 kg of Nympheal was prepared by electrophilic bromination of 1-isobutyl-3-methylbenzene, followed by reaction with magnesium and dimethylformamide to give the corresponding benzaldehyde, which was then reacted with ethyl vinyl ether by the procedure from Muller-Cunradi–Pierroh and hydrogenated to give the desired product.

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“…10,[31][32][33][34] The regiochemistry of the oxidation, however, may be difficult to control and the conditions may occasionally give rearrangement products, especially in sterically crowded environments. 35,36 Regardless, the synthesis of all-carbon fully fused materials has been heavily dependent on Scholl oxidation. This argument also holds true in smaller oligomers.…”

Section: Kinetic Annulationsmentioning

confidence: 99%

Annulation Reactions for Conjugated Ladder-Type Oligomers

Kalin

Lee

Fang

2018

Synlett

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Conjugated ladder-type oligomers are a class of important functional organic materials. They possess intriguing properties stemming from their fully fused aromatic backbones. The construction of the ladder-type backbone relies on a ‘ladderization’ step, which may be accomplished through either kinetically or thermodynamically controlled annulation reactions. The attributes of these reactions are discussed, with relevant recent examples. The development of these reactions is key to continued advances and innovation in the field of organic conjugated materials.1 Introduction2 Kinetic Annulations3 Thermodynamic Annulations4 Future Outlooks and Conclusion

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Discovery of Deep-Seated Skeletal Rearrangements in the Photocyclizations of Some tert-Butyl-Substituted 1,2-Diarylethylenes

Cited by 16 publications

References 14 publications

Synthesis of multi ring-fused imidazo [1,2-a]isoquinoline-based fluorescent scaffold as anti-Herpetic agent

Synthesis of multi ring-fused imidazo [1,2-a]isoquinoline-based fluorescent scaffold as anti-Herpetic agent

Process Research and Scale-Up Synthesis of 3-(4-Isobutyl-2-methylphenyl)propanal, a Safe and Uniquely Performing Perfumery Ingredient

Annulation Reactions for Conjugated Ladder-Type Oligomers

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