Photochemical O−H Functionalization Reactions of Cyclic Diazoamides

Empel, Claire; Verspeek, Dennis; Jana, Sripati; Koenigs, René M.

doi:10.1002/adsc.202000818

Cited by 29 publications

(21 citation statements)

References 34 publications

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“…Subsequent nucleophilic substitution gives desired product 84 . The first report on this topic concerns the reaction of aryl/EWG diazo compounds 9 with fluorinated alcohols 85 , but it works well also for chlorinated and brominated compounds (Scheme B), as well as for cyclic diazo amides 87 (Scheme C) . This transformation gives access to a range of halogenated, mainly fluorinated, ethers 88 which are formed in high to excellent yields.…”

Section: X–h Insertionsmentioning

confidence: 99%

“…The first report on this topic concerns the reaction of aryl/EWG diazo compounds 9 with fluorinated alcohols 85, but it works well also for chlorinated and brominated compounds (Scheme 23B), 61 as well as for cyclic diazo amides 87 (Scheme 23C). 62 This transformation gives access to a range of halogenated, mainly fluorinated, ethers 88 which are formed in high to excellent yields. Importantly, the same reaction was examined in the dark in the presence of Cu and Rh catalysts, typically used to generate metal carbene species, but no product formation was observed.…”

Section: -Pyridone C (Scheme 22bmentioning

confidence: 99%

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Lightening Diazo Compounds?

Durka

Turkowska

Gryko

2021

ACS Sustainable Chem. Eng.

171

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The development of new sustainable reactions and protocols is essential to fulfill the growing demands of every branch of organic chemistry for greener synthetic methodologies. In this context, the use of visible light as the only source of energy is highly appealing. Since diazo compounds are valuable reagents in organic synthesis, their transformations realized in a sustainable manner are of interest. High reactivity and easy availability make them suitable for solar-driven transformations. Indeed, photochemical reactions of diazo compounds have recently proven a valuable alternative to transition metal catalysis. In this perspective, we highlight applications of these reagents under visible irradiation, particularly focusing on recent advancements. These include photochemical generation of carbenes and radicals which involve many relevant reactions, [2+1]-cycloadditions, X−H and C−H insertions, Wolff rearrangement, and more. Mechanistic aspects of these processes are briefly addressed to give readers a deeper understanding of rules underlying photoreactivity of diazo compounds. We conclude by emphasizing significant advancements and discussing challenges for future developments in the photochemistry of these valuable reagents.

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Section: X–h Insertionsmentioning

confidence: 99%

Section: -Pyridone C (Scheme 22bmentioning

confidence: 99%

Lightening Diazo Compounds?

Durka

Turkowska

Gryko

2021

ACS Sustainable Chem. Eng.

171

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“…Refluxing in DCE at 100 °C for 6 h produced O−H insertion product ( 7 ) in 95% yield (Scheme 2, a ). These results indicate that the additive benzoic acid is not competitive for N ‐methoxybenzamide and N ‐methoxybenzamide is more reactive than benzoic acid in C−H activation [16] . A competition experiment between N ‐methoxyarylamides was performed (Scheme 2, b ).…”

Section: Resultsmentioning

confidence: 95%

Rhodium(III)‐Catalyzed Sequential C−H Activation and Cyclization from N‐Methoxyarylamides and 3‐Diazooxindoles for the Synthesis of Isochromenoindolones

Maeng

Jeong

et al. 2021

Chemistry An Asian Journal

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An efficient synthetic method for structurally various isochromenoindolones has been demonstrated through Rh(III)‐catalyzed C−H activation followed by a cyclization reaction of N‐methoxyarylamides with 3‐diazooxindoles. The sequential reaction involves the streamlined formation of C−C and C−O bonds in one pot. The present method provides a broad range of isochromenoindolones as a new privileged scaffold in moderate to good yields with the release of methoxyamine and molecular nitrogen and has the benefits of a broad substrate scope and good functional group tolerance.

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“…Koenigs et al could also demonstrate the application of such photoexcited proton transfer reactions towards cyclic diazoamides demonstrating broad applicability of such reactions. 73…”

Section: Photochemical Applications Of Diazoalkanesmentioning

confidence: 99%