Radical azidation reactions and their application in the synthesis of alkaloids

This Perspective illustrates the defining characteristics of free radical chemistry, beginning with its rich and storied history. Studies from our laboratory are discussed along with recent developments emanating from others in this burgeoning area. The practicality and chemoselectivity of radical reactions enable rapid access to molecules of relevance to drug discovery, agrochemistry, material science, and other disciplines. Thus, these reactive intermediates possess inherent translational potential, as they can be widely used to expedite scientific endeavors for the betterment of humankind.

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“… 55 Radical-based azide transfer, emerging from Renaud’s laboratory, forges C–N bonds with efficiency and selectivity. 56 …”

Section: Introduction and Historical Contextmentioning

confidence: 99%

Radicals: Reactive Intermediates with Translational Potential

et al. 2016

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“…The azidation process is efficient with nucleophilic radicals and does not occur with ambiphilic or electrophilic radicals. The resulting functionalized organic azide, upon reduction or rearrangement, provides access to valuable nitrogen‐containing intermediates for alkaloid synthesis . To promote the process, 3‐pyridinesulfonyl azide (phenylsulfonyl azide in the first generation), hexabutylditin (as the chain transfer reagent), and an α‐(halo or xanthate)acetate or an α‐haloketone (as the radical precursor) are commonly used (Scheme ).…”

Section: From Alkenes and Alkynesmentioning

confidence: 99%

Radical Reactions in Alkaloid Synthesis: A Perspective from Carbon Radical Precursors

Bonjoch

Diaba

2020

Eur J Org Chem

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The usefulness of radical reactions in alkaloid synthesis is reviewed from the perspective of the functional groups embedded in the molecular structure of synthetic intermediates, that act as precursors of carbon‐centered radicals in the construction of new C–C bonds. The functional groups featured are alkenes, alkynes, halides (alkyl, vinyl, aryl), xanthates, sulfides, selenides, aldehydes, ketones, carboxylic acid derivatives (selenoesters, haloacetamides), β‐dicarbonyl compounds, and α‐heterosubstituted nitrogen‐compounds. The use of nitrogen‐centered radicals for C–N bond formation is also covered. Among the variety of radical processes applied, the most predominant are the hydride reductive method (Sn, Si), atom transfer radical reactions (Cu, Ru, B), and single‐electron transfer radical reactions promoted by Sm, Ni, Fe, Mn, Ti, and Ag. This review showcases the role radical reactions have played in the recent development of new strategies in alkaloid synthesis, as well as the implementation of new radical procedures in demanding substrates.

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“…Renaud and co-workers reported the formal synthesis of (±)-lepadiformine C [(±)-16] utilizing radical carboazidation of an alkene (Scheme 17), 51,52 which was an updated protocol from their previous synthesis of (±)-lepadiformine A [(±)-14]. 53 The key carboazidation was initiated from the reaction of sulfonyl azide 111 with di-tert-butyldiazene to generate electrophilic α-carbonyl radical 112, that reacted with the exomethylene moiety of the B-ring synthon 113 to give alkyl radical 114.…”

Section: From B Ringmentioning

confidence: 99%

Synthesis of Tricyclic Marine Alkaloids, Cylindricines, Lepadiformines, Fasicularin, and Polycitorols: A Recent Update

Kaga

Chiba

2017

Synthesis

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Cylindricines, lepadiformines, and fasicularin are tricyclic marine alkaloids bearing perhydropyrrolo- and pyrido[2,1-j] frameworks having divergent chemical functionalities. They have been isolated from marine tunicates over the last two decades and found to have a range of cytotoxicity such as DNA-alkylating ability. Recently, polycitorols have emerged as a new member of this alkaloid family. Their unique structural features and biological activities have intrigued many researchers and challenged them in their synthesis. This review describes recent syntheses of the tricyclic alkaloids based on key synthetic approaches.1 Introduction2 Total and Formal Syntheses2.1 Overview of Synthetic Strategies2.2 Azaspirocycle (BC Ring) Approaches2.3 Indolizidine (AC Ring) Approaches2.4 Azadecalin (AB Ring) Approaches2.5 Tandem Cyclization Approaches3 Summary and Future Perspective

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Radical azidation reactions and their application in the synthesis of alkaloids

Cited by 55 publications

References 46 publications

Radicals: Reactive Intermediates with Translational Potential

Radicals: Reactive Intermediates with Translational Potential

Radical Reactions in Alkaloid Synthesis: A Perspective from Carbon Radical Precursors

Synthesis of Tricyclic Marine Alkaloids, Cylindricines, Lepadiformines, Fasicularin, and Polycitorols: A Recent Update

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