Functionalized spirolactones by photoinduced dearomatization of biaryl compounds

Li, Hongji; Subbotina, Elena; Bunrit, Anon; Wang, Feng; Samec, Joseph S. M.

doi:10.1039/c8sc05476b

Cited by 54 publications

(43 citation statements)

References 47 publications

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“…The dearomatization could also be carried out by employing sodium trifluoromethanesulfonate as reactant in 62% yield (6 e). What's more, the selective C2 trifluoromethylation product 6 f was obtained in 41% yield using mixed solvent of DMSO and CH 3…”

Section: Resultsmentioning

confidence: 99%

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Electrochemical Selective Oxidative Functionalization of Caffeine

et al. 2020

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Direct electrochemical oxidative functionalization of caffeine under metal‐free and external‐oxidant‐free conditions was achieved. Nucleophiles such as various substituted pyrazoles, alcohols, and sodium trifluoromethanesulfonate can be utilized with high diastereoselectivity for the dearomatizative functionalization of caffeine. In addition, selective C2 functionalization of caffeine has also been realized with the modification of solvent and reaction time. A gram‐scale experiment demonstrates the potential application in the derivatization of caffeine.

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Section: Resultsmentioning

confidence: 99%

“…[2] On the other hand, selective dearomatizative functionalization of heterocycles remains a challenge in organic synthesis. [3] In recent years, some strategies concerning the dearomatizative functionalization of indole have been reported. [4] However, stoichiometric chemical oxidants are normally essential for these conversions.…”

Section: Introductionmentioning

confidence: 99%

Electrochemical Selective Oxidative Functionalization of Caffeine

et al. 2020

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“…From this moment, synthetic chemists are constantly trying to design reasonable substrates or develop novel strategies in the field of intramolecular radical dearomative spirocyclization. To date, several groups have independently explored and established intramolecular radical dearomative spirocyclization with oxygen promotion or visible‐light irradiation (Scheme 24d–f) [40f–j] . In 2013, an efficient and green intramolecular oxidative coupling of phenol for the direct construction of 108 was developed by the group of Wang, in which utilizing environment‐friendly sodium nitrite as the catalyst and air oxygen as the terminal oxidant (Scheme 24e) [40f] .…”

Section: Intramolecular Cyclizationmentioning

confidence: 99%

“…In the same year, Wang and Samec's group also achieved an intramolecular radical dearomative spirocyclization of nonphenolic biaryl carboxylic acids 121 , leading to the spirolactones 122 (Scheme 27). [40i] This protocol could be performed vi a either aerobic photocatalysis or anaerobic photooxidation to tolerate specific synthetic conditions, in which dearomatization was induced by a 5‐ exo ‐trig spirocyclization with the addition of the carboxyl radical 123 . The resulting intermediate 124 was captured by either oxygen or water in aerobic and anaerobic systems, respectively, to obtain the spirodienone 122 .…”

Section: Intramolecular Cyclizationmentioning

confidence: 99%

Recent Advances in the Construction of Spiro Compounds via Radical Dearomatization

2020

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The field in dearomatization of aromatic compounds for the construction of spirocycle compounds has been developed rapidly over the last two decades and it provides alternative synthetic method without using extra stoichiometric amounts of chemical oxidants or reductants. In addition, the radical cascade reactions of alkenes or alkynes that produce multiple chemical bonds in one-step are significant in the direct and efficient building of complex molecules. By combining these two concepts, dearomatization and radical cascade reactions of alkenes or alkynes opens a new and powerful avenue in accessing spirocycle molecules. These cascade reactions have been well explored in the past decade. As a result, we summarize recent eventful advances in this rapidly growing area as a review, in which the typical examples are listed and mechanism are also discussed.

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“…In either case, dearomatization was prompted via electrophilic attack of the carboxyl radicals. Further, the spirodiene radical generated was quenched by either water or oxygen (Scheme ) …”

Section: Synthetic Strategies Towards Spirobutenolides and Spirobutyrmentioning

confidence: 99%

Natural and Synthetic Spirobutenolides and Spirobutyrolactones

Yadav

Pratap

Ram³

2020

Asian J Org Chem

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Spirobutenolides and spirobutyrolactones structural motifs are widespread in various natural products that exhibit a broad array of biological activities. Additionally, their synthetic analogues also serve as biologically active compounds and building blocks of complex molecules. Owing to the wide range of pharmacological activities and structural diversity of the spirobutenolides and spirobutyrolactones, various efficient synthetic methodologies have been established to construct such interesting scaffolds. In the past decades, numerous total syntheses of spirobutenolides and spirobutyrolactones containing natural products have been reported. Structurally diverse spirobutenolides and spirobutyrolactones have been synthesized by using singlet oxygen, Mannich reaction, aldol condensation, rearrangement reaction , Reformatsky reaction, Michael-addition cyclization, Diels-Alder reaction, photocyclization reaction, and pericyclic reactions. Recently, metal-catalyzed cyclization, photocatalyzed radical cyclization, Baylis-Hillman reaction, asymmetric organocatalysis, NHC catalysis, ring contraction reactions, and hypervalent iodine catalysis have emerged as powerful tools to architect these nuclei. This review gives an overview of advancements in chemically and biologically relevant spirobutenolides and spirobutyrolactones of natural and synthetic origin. It also covers the newer methodologies for the construction of natural as well as synthetic spirobutenolides and spirobutyrolactones along with their potential applications.

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Functionalized spirolactones by photoinduced dearomatization of biaryl compounds

Abstract: Visible-light-induced dearomatization of non-phenolic 1,1′-biaryl-2-carboxylic acids has been developed by either aerobic photocatalytic or anaerobic photooxidative pathways.

Cited by 54 publications

References 47 publications

Electrochemical Selective Oxidative Functionalization of Caffeine

Electrochemical Selective Oxidative Functionalization of Caffeine

Recent Advances in the Construction of Spiro Compounds via Radical Dearomatization

Natural and Synthetic Spirobutenolides and Spirobutyrolactones

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