Synthesis of Perinaphthenones via BF3.Et2O Mediated One‐Pot Cascade 4,5‐Annulation Reactions of 1‐Naphthols and Ynones

Kuo, Chun Wei; Rao, Naidu Sambasiva; Patil, Prakash Bhimrao; Chiang, Ting Ta; Kavala, Veerababurao; Yao, Ching Fa

doi:10.1002/adsc.202001558

Cited by 5 publications

(3 citation statements)

References 47 publications

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“…Phenalenones and their derivatives have rich photophysical properties, , and they are known as good singlet oxygen photosensitizers. − Substituents on phenalenones and structural variations can strongly influence the photosensitizing properties. , Inspired by our library of structurally diverse functionalized phenalenones, we explored the relationships between their structure and properties. To compare the photophysical properties for the isomeric conjugated ketones, we analyzed absorbance and emission spectra for selected compounds (Figure ).…”

Section: Results and Discussionmentioning

confidence: 99%

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Tethering Three Radical Cascades for Controlled Termination of Radical Alkyne peri-Annulations: Making Phenalenyl Ketones without Oxidants

Hu,

Kuhn,

Makurvet

et al. 2024

J. Am. Chem. Soc.

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Although Bu3Sn-mediated radical alkyne peri-annulations allow access to phenalenyl ring systems, the oxidative termination of these cascades provides only a limited selection of the possible isomeric phenalenone products with product selectivity controlled by the intrinsic properties of the new cyclic systems. In this work, we report an oxidant-free termination strategy that can overcome this limitation and enable selective access to the full set of isomerically functionalized phenalenones. The key to preferential termination is the preinstallation of a “weak link” that undergoes C–O fragmentation in the final cascade step. Breaking a C–O bond is assisted by entropy, gain of conjugation in the product, and release of stabilized radical fragments. This strategy is expanded to radical exo-dig cyclization cascades of oligoalkynes, which provide access to isomeric π-extended phenalenones. Conveniently, these cascades introduce functionalities (i.e., Bu3Sn and iodide moieties) amenable to further cross-coupling reactions. Consequently, a variety of polyaromatic diones, which could serve as phenalenyl-based open-shell precursors, can be synthesized.

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Section: Results and Discussionmentioning

confidence: 99%

“…Photophysical Properties. Phenalenones and their derivatives have rich photophysical properties, 157,158 and they are known as good singlet oxygen photosensitizers. 159−164 Substituents on phenalenones and structural variations can strongly influence the photosensitizing properties.…”

Section: Role Of Thermodynamics In Radical Fragmentationmentioning

confidence: 99%

Tethering Three Radical Cascades for Controlled Termination of Radical Alkyne peri-Annulations: Making Phenalenyl Ketones without Oxidants

Hu,

Kuhn,

Makurvet

et al. 2024

J. Am. Chem. Soc.

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“…[31] The Yao research group has successfully synthesized perinaphthenones from 1-naphthols and ynones utilizing BF 3 * Et 2 O (Scheme 26). [32] This one-pot cascade reaction involves the dearomative C4À C5 periannulation of 1-naphthols and ynones, ultimately leading to the formation of photo-physically active perinaphthenones.…”

Section: Synthesis Of Carbo-and Hetero-cycle Substituted Indolesmentioning

confidence: 99%

Indolyl‐Ynones: Building Blocks for Molecular Diversity

Behera

2024

Adv Synth Catal

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This review centers on the synthetic strategies employed with indolyl‐ynones. Indolyl‐ynone, owing to its highly reactive ynone moiety, frequently partakes in dearomatizing spirocyclization reactions and subsequent rearrangment reactions when subjected to various reaction conditions. Hence, various heterocycles such as densly functionalized spiroindolenines, carbazoles, quinolines and carbo‐and hetero‐cycle substituted indoles are synthesized from indolyl‐ynones. In addition to this, the versatile spirocyclic indole scaffold exhibits the capability to produce tetracyclic and polyclic structures through intricate skeletal rearrangement processes. Moreover, the total synthesis of natural products using the indolyl‐ynone moiety was also compiled in this review.

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Stable peri‐Naphthoisatogens without C2 Protection: Synthesis via Aldrone Condensation, Optical Properties and 1,3‐Dipolar Cycloaddition Reaction

Debnath,

Roy,

Borah

et al. 2023

Chemistry An Asian Journal

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Abstractperi‐Annulation of naphthalane, an important tool for realization of wide range of functional materials, is presently accomplished with limited few functional groups like imide, amide and diamine‐derivative (perimidine). To increase the diversity, we have incorporated α‐keto aldonitrone as a new functional group, and herein report about five peri‐naphthoisatogens (PNTIs) dyes. The synthesis were accomplished using an unusual reaction of aromatic nitro group, which is nucleophilic attack of a C‐nucleophile (enol) to the N‐atom of nitro group. In five different 5‐alkylamino‐8‐nitro‐1‐acetylnaphthalenes, intramolecular acid‐catalyzed nucleophilic attack of enol moiety to the N‐atom of nitro group produced α‐keto aldonitrone via addition‐elimination mechanism. The PNTIs showed characteristics of 1,3‐dipole and reacted with ethyl acrylate to produce isoxazolidine ring, which subsequently converted into aza phenalenone derivative via ring cleavage. Both the PNTI and the corresponding derivative strongly absorb in the visible region, displaying absorption maximum at 551 and 561 nm (in CHCl3) respectively. Compared to the popular analogous dye naphthalene monoimides, PNTIs showed bathochromic shift of absorption maximum by more than 100 nm. The emission maximum for the PNTI and its derivative in chloroform were observed at 594 and 635 nm respectively.

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Synthesis of Perinaphthenones via BF₃^.Et₂O Mediated One‐Pot Cascade 4,5‐Annulation Reactions of 1‐Naphthols and Ynones

Cited by 5 publications

References 47 publications

Tethering Three Radical Cascades for Controlled Termination of Radical Alkyne peri-Annulations: Making Phenalenyl Ketones without Oxidants

Tethering Three Radical Cascades for Controlled Termination of Radical Alkyne peri-Annulations: Making Phenalenyl Ketones without Oxidants

Indolyl‐Ynones: Building Blocks for Molecular Diversity

Stable peri‐Naphthoisatogens without C2 Protection: Synthesis via Aldrone Condensation, Optical Properties and 1,3‐Dipolar Cycloaddition Reaction

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