Tandem Aryne‐Capture/Sigmatropic Rearrangement as a Metal‐Free Entry to Functionalized <i>N</i>‐Aryl Pyrrolidines

Moss, Sam G.; Pocock, Ian A.; Sweeney, Joseph B.

doi:10.1002/chem.201605290

Cited by 30 publications

(4 citation statements)

References 101 publications

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“…In 2017, Sweeney and co-workers applied this aryne-induced [2,3] Stevens rearrangement protocol on N-(2-malonyl) tetrahydropyridines 9-104 and furnished 3-substituted Naryl-2-acylpyrrolidines 9-105 in modest to excellent yields (Scheme 176a). 673 Moreover, Liu et al employed 1,2,3,4tetrahydroisoquinolines 9-106 as the substrates to readily prepare (E)-3-aryl-2,3,4,5-tetrahydro-1H-3-benzazonines 9-107 in highly stereospecific manner (Scheme 176b). 674 In 2018, Tian and co-workers reported an aryne-induced [2,3] Stevens rearrangement with tertiary propargylic amines 9-108 bearing electron-withdrawing groups (Scheme 176c).…”

Section: Cascade or Tandem Reactionsmentioning

confidence: 99%

o-Silylaryl Triflates: A Journey of Kobayashi Aryne Precursors

2021

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Arynes are among the most active organic intermediates and have found numerous applications in expeditious preparation of substituted arenes. In the past 20 years, chemists have witnessed a resurgence in aryne chemistry, which is mainly attributed by the extensive utilization of Kobayashi's method, a fluoride-induced removal of the TMS group with concomitant departure of its ortho OTf group on o-silylaryl triflates. Nowadays, o-silylaryl triflates are the most frequently employed aryne precursors. This review provides an overview of the history of Kobayashi's method, its methodological achievements, and its applications in the synthesis of natural products, bioactive molecules, and polycyclic aromatic hydrocarbons.

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Section: Cascade or Tandem Reactionsmentioning

confidence: 99%

o-Silylaryl Triflates: A Journey of Kobayashi Aryne Precursors

2021

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“…Because of its exceptionally high reactivity, benzyne be a certain way produced in situ from its forerunner and quickly captured by adequate arynophiles. Otherwise, it will easily decompose on its own [3]. The most representative generation of arynes involves the dissolution of an orthogonal-departing group via an aryl anion species.…”

Section: Introductionmentioning

confidence: 99%

Arynes in Natural Product Synthesis

Martin¹,

Bharti²

2023

IJRASET

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Arynes are a unique class of intermediates used in synthetic organic chemistry, and research interest has been intensely focused on their peculiar reactivities. Arynes have been researched for almost a century. However, difficulties in monitoring these reactive species, as well as difficulties in creating synthetically viable techniques for their synthesis and trapping, have restricted their application. A key tactic for achieving the racemic and enantiopure total synthesis of a broad variety of natural compounds or their structural derivatives. The chemistry of arynes has advanced significantly over the past thirty years, particularly in the field of transition metal carbon- carbon and carbon-heteroatom bond-forming mechanisms. The field’s fast growth is largely attributable to the development of mild aryne production processes. To create a natural product with complex organic molecules, the role of aryne intermediates was non-replaceable. These organic substances are often used in medicine, therapies, or as raw material for the synthesis of other substances. Moreover, they may perform important biological tasks. There are numerous methods for synthesizing natural compounds including total synthesis, semi-synthesis, and biosynthesis. Total synthesis is the process of creating natural products entirely chemically from basic precursors as well as it can be produced in large quantities and can reveal information about its biological activity. One of the developments in Arynes’ chemistry is the chemical rearrangements brought about by this electrophilic intermediate. It is not feasible to use conventional methods in a single step. This review article discusses how arynes are used to create natural products. Arynes has a wide range of functionality in the field of scientific research. The evolution of this method has made a tremendous change in the total synthesis of natural products. Benzynes enabled creative synthesis in mild conditions. The transformation has expanded to investigate various reaction classes such as nucleophilic addition, (4+2), and (2+2) cycloaddition strategies and metal-catalyzed reactions are shown and explained in this article. This review will provide an idea about how the arynes act as an intermediate in those reaction mechanisms and enlighten the scope of these aryne intermediate.

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“…We have recently demonstrated the generation of strained aziridinium ylide A by the reaction of arynes with N -substituted aziridines, and the formed ylide was trapped with aldehydes for the diastereoselective synthesis of 2-amino epoxides (eq 2). , Inspired by the work of Hwu and co-workers, we envisioned that the nitrogen ylide generated from the Schiff base and aryne could be intercepted with tropone in a [6 + 3] annulation reaction for convenient access to azabicyclo[4.3.1]decadienes. This three-component coupling is likely to proceed via the initial formation of the 1,4-zwitterion B from the Schiff base and aryne, which could undergo a proton transfer to form the nitrogen ylide C , and a subsequent [6 + 3] annulation could result in the formation of the bicyclic products (eq 3).…”

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confidence: 99%

Three-Component, Diastereoselective [6 + 3] Annulation of Tropone, Imino Esters, and Arynes

et al. 2021

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A transition-metal-free, three-component, and diastereoselective [6 + 3] annulation reaction employing tropone, imino esters, and arynes allowing the synthesis of bridged azabicyclo[4.3.1]decadienes is demonstrated. The key nitrogen ylides for the [6 + 3] annulation were generated by the addition of imino esters to the arynes followed by a proton transfer. The nitrogen ylides undergo a regioselective addition to tropone to furnish the desired products in moderate to good yields with good functional group tolerance under mild conditions.

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Tandem Aryne‐Capture/Sigmatropic Rearrangement as a Metal‐Free Entry to Functionalized N‐Aryl Pyrrolidines

Cited by 30 publications

References 101 publications

o-Silylaryl Triflates: A Journey of Kobayashi Aryne Precursors

o-Silylaryl Triflates: A Journey of Kobayashi Aryne Precursors

Arynes in Natural Product Synthesis

Three-Component, Diastereoselective [6 + 3] Annulation of Tropone, Imino Esters, and Arynes

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