Unlocking novel reaction pathways of diazoalkanes with visible light

Empel, Claire; Cao, Ping; Koenigs, René M.

doi:10.1039/d1cc06521a

Cited by 82 publications

(49 citation statements)

References 79 publications

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“…Generally, visible0light-induced chemical transformations of diazo compounds can be roughly divided into the following two categories. The first one is the photolysis of diazo compounds, with the formation of electrophilic carbene species (Scheme a, left) . Those reactions generally occurred under solely visible-light irradiation without the addition of photoredox catalysts and have been extensively investigated for building complicated organic molecules.…”

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confidence: 99%

Photochemical Synthesis of Succinic Ester-Containing Phenanthridines from Diazo Compounds as 1,4-Dicarbonyl Precursors

Zhou

et al. 2022

Org. Lett.

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We disclosed herein a straightforward photochemical method for the construction of phenanthridines containing a synthetically useful succinate unit. The reaction occurred under visible-light irradiation with cheap eosin Y Na as photoredox catalyst and a diazo compound as the succinate precursor. Under the optimal reaction conditions, a wide range of phenanthridines were obtained in moderate to good yields. Note that the succinate units in the final heterocycles could be easily transformed into many valuable structures, such as γ-butyrolactone, dihydrofuran-2(3H)-one, and tetrahydrofuran. Mechanistic experiments were performed to support the proposed mechanism.

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confidence: 99%

Photochemical Synthesis of Succinic Ester-Containing Phenanthridines from Diazo Compounds as 1,4-Dicarbonyl Precursors

Zhou

et al. 2022

Org. Lett.

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“…Almost complete conversion of substrate 1 was observed, in contrast to the catalyst-free experiment (Scheme 2). Dimethyl carbonate (8), cyclohexanone (9), and cyclohexene (10) were identified as main products, with the latter one resulting from the 1,2-H migration, a transformation typical for alkylidene carbenes, 33 suggesting its formation in a triplet energy transfer process. Cyclopropanation -optimization studies.…”

Section: Resultsmentioning

confidence: 99%

UV Light is no Longer Required for the Activation of 1,3,4-Oxadiazolines

Orłowska

Santiago

Krajewski

et al. 2022

Preprint

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Carbenes play a key role in a plethora of organic transformations. Although stabilized diazo carbonyl compounds predominate as a source of electrophilic carbenes, the hazardous nature of non-stabilized analogues calls for their in situ generation from stable precursors. Among these, 1,3,4-oxadiazolines serve as diazoalkane surrogates under UV light irradiation. In view of their diverse reactivities and straightforward synthesis, milder methodologies for the activation of these compounds, that permit the use of UV light-sensitive substrates, are of high significance. Herein, we report the visible-light-induced activation of oxadiazolines by triplet energy transfer catalysis that, in contrast to UV-induced processes, enables generation of carbenes. The formed reactive species react with electron-poor olefins, giving valuable spirocyclopropanes. Mechanistic investigations, both theoretical and experimental, uncover plausible pathways and highlight the importance of the triplet energy-transfer steps.

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“…An alternative method for the generation of carbenes is the photochemical decomposition of diazoalkanes . Various diazo esters absorb light in the visible region to generate the corresponding carbene following loss of nitrogen.…”

Section: Use Of Carbenes In Continuous Flowmentioning

confidence: 99%

Continuous Flow Technology as an Enabler for Innovative Transformations Exploiting Carbenes, Nitrenes, and Benzynes

Donnelly

Baumann

2022

J. Org. Chem.

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Miniaturization offered by microreactors provides for superb reaction control as well as excellent heat and mass transfer. By performing chemical reactions in microreactors or tubular systems under continuous flow conditions, increased safety can be harnessed which allows exploitation of these technologies for the generation and immediate consumption of high-energy intermediates. This Synopsis demonstrates the use of flow technology to effectively exploit benzynes, carbenes, and nitrenes in synthetic chemistry programs.

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Unlocking novel reaction pathways of diazoalkanes with visible light

Abstract: Photochemistry has recently attracted the interest of synthetic chemists to conduct photolysis reactions of diazoalkanes. In this feature article, we provide a concise overview on this field, starting with discoveries...

Cited by 82 publications

References 79 publications

Photochemical Synthesis of Succinic Ester-Containing Phenanthridines from Diazo Compounds as 1,4-Dicarbonyl Precursors

Photochemical Synthesis of Succinic Ester-Containing Phenanthridines from Diazo Compounds as 1,4-Dicarbonyl Precursors

UV Light is no Longer Required for the Activation of 1,3,4-Oxadiazolines

Continuous Flow Technology as an Enabler for Innovative Transformations Exploiting Carbenes, Nitrenes, and Benzynes

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