Synthesis and Utilization of Nitroalkyne Equivalents in Batch and Continuous Flow

Morse, Peter D.; Jamison, Timothy F.

doi:10.1002/anie.201706157

Cited by 21 publications

(8 citation statements)

References 51 publications

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“…183 In 2017, Morse and Jamison used nitronium triflate as a reagent using batch and flow chemistry techniques for the nitration of TMS-acetylenes 315 to provide nitrated silyl triflates 316 as stabilized nitroalkyne equivalents (Scheme 83). 184 Subsequent elimination/dipolar cycloaddition reactions of 316 with nitrones gave highly substituted 4-nitro-4-isoxazolines 317 in high yields.…”

Section: Organic Nitronium Saltsmentioning

confidence: 99%

Organic Nitrating Reagents

Patra¹,

Mosiagin²,

Katayev³

et al. 2022

Synthesis

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Nitro compounds are vital raw chemicals that are widely used in academic laboratories and industries for the preparation of various drugs, agrochemicals, and materials. Thus, nitrating reactions are of great importance for chemists and are even taught in schools as one of the fundamental transformations in organic synthesis. Since the discovery of the first nitrating reactions in the 19th century, progress in this field has been constant. Yet, for many years the classical electrophilic nitration approach using a mixture of strong mineral acids dominated the field. However, in recent decades, the attention of researchers has focused on new reactivity and new reagents that can provide access to nitro compounds in a practical and straightforward way under mild reaction conditions. Organic nitrating reagents have played a special role in this field since they have enhanced reactivity. They also allow nitration to be carried out in an ecofriendly and sustainable manner. This review examines the development and application of organic nitrating reagents.1 Introduction2 Organic Nitrating Reagents2.1 Alkyl Nitrites2.2 Nitroalkanes2.3 Alkyl Nitrates2.4 N-Nitroamides2.5 N-Nitropyrazole2.6 N-Nitropyridinium Salts3 Organic Nitrating Reagents Generated In Situ3.1 Acyl Nitrates3.2 Trimethylsilyl Nitrate3.3 Nitro Onium Salts4 Organic Nitronium Salts5 Organic Nitrates and Nitrites5.1 Ammonium Nitrates5.2 Heteroarylium Nitrates5.3 Other Organic Nitrates5.4 Organic Nitrites6 Conclusion and Outlook

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Section: Organic Nitronium Saltsmentioning

confidence: 99%

Organic Nitrating Reagents

Patra¹,

Mosiagin²,

Katayev³

et al. 2022

Synthesis

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“…The flow protocol is able to carry out the entire reaction sequence in a good yield and a short residence time, minimizing the accumulation of potentially hazardous reaction intermediates. The entire process (generation of nitronium triflate, formation of the vinyl silyltriflate intermediate and [3+2] cycloaddition) lasts 21 min and gives good yield (Scheme ) …”

Section: ‐Membered Ringsmentioning

confidence: 99%

Flow Chemistry for Cycloaddition Reactions

2020

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Continuous flow reactors form part of a rapidly growing research area that has changed the way synthetic chemistry is performed not only in academia but also at the industrial level. This Review highlights the most recent advances in cycloaddition reactions performed in flow systems. Cycloadditions are atom-efficient transformations for the synthesis of carbo-and heterocycles, involved in the construction of challenging skeletons of complex molecules. The main advantages of translating these processes into flow include using intensified conditions, safer handling of hazardous reagents and gases, easy tuning of reaction conditions, and straightforward scaling up. These benefits are especially important in cycloadditions such as the copper(I)-catalyzed azide alkyne cycloaddition (CuAAC), Diels-Alder reaction, ozonolysis and [2 + 2] photocycloadditions. Some of these transformations are key reactions in the industrial synthesis of pharmaceuticals.

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“…Recently, the generation of silyl triflates 57A derived from trimethylsilyl alkynes 57 as equivalents of nitro alkynes was reported by Jamison and co-worker in batch and continuous flow (Scheme 21). [52] Nitro alkynes suffer from poor stability and the application in organic synthesis appeared to be illusive. Jamison's group reported that treatment of alkynes 57 with a solution of nitronium triflate in sulfolane leads to the in situ formation of nitro alkynes 57B, which smoothly undergo [3+2] cycloaddition with nitrones to form stable 4-nitro-4-isoxazolines (58).…”

Section: Scheme 20 Fluorination Of Diarylacetylenesmentioning

confidence: 99%