Dearomatization and Aryl Migration in Organolithium Chemistry

Clayden, Jonathan

doi:10.1002/9783527667512.ch13

Cited by 6 publications

(5 citation statements)

References 70 publications

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“…Addition of organolithium reagents to arenes, leading to dearomatization, is now an important synthetic tool, but to our knowledge, so far, it has not been applied for pyrene functionalization.…”

mentioning

confidence: 60%

Alkylation of the K-Region in a Sterically Hindered Pyrene Carboxamide via Directed Reaction with Alkyllithiums under Air

et al. 2018

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Sterically hindered N,2,7-tri-tert-butylpyrene-1-carboxamide treated with n-BuLi, i-BuLi, s-BuLi, and n-HexLi in THF in the presence of TMEDA and air afforded trans-N,2,7-tri-tert-butylpyrene-10-alkyl-9-hydroxy-9,10-dihydropyrene-1-carboxamides in 63–74% yield. Trifluoroacetic acid promoted dehydration of these compounds gave 10-alkyl derivatives of the starting amide in 79–89% yield. The minor products of this reaction were deamidated compounds, 4-alkyl-2,7-di-tert-butylpyrenes.

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mentioning

confidence: 60%

Alkylation of the K-Region in a Sterically Hindered Pyrene Carboxamide via Directed Reaction with Alkyllithiums under Air

et al. 2018

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“…Most of the reported literature with organolithium reagents focuses the attention on the solvent effect on the aggregation state of the lithiating agent, [1,2] but only a few examine how this effect changes the product distribution. [16,17] The nature of the solvent could affect the stability of some of the intermediates and also the dynamic equilibrium, favoring the formation of new products and/or increasing the yield of formerly minor products.…”

Section: Solvent Effectsmentioning

confidence: 99%

“…Tandem sequences involving halogen/lithium exchange and intramolecular carbolithiation-cyclization-electrophilic substitution provide fascinating approaches to challenge synthetic issues. [1,2] The carbolithiation reaction attracts the interest of synthetic organic chemists, as it offers a convenient pathway for the efficient building of new carbon-carbon bonds by addition of an organolithium reagent to nonactivated alkenes or alkynes, and the possibility of introducing further functionalization on the molecule by trapping the reactive organolithium intermediate with electrophiles. [3] The subtle control of chemoselectivity, regioselectivity, and stereoselectivity achievable within carbolithiation points the way toward exciting applications in carbocyclic, heterocyclic, alkene, and alkane synthesis.…”

Section: Introductionmentioning

confidence: 99%

Intramolecular carbolithiation‐cyclization‐electrophilic substitution: solvent effect and mechanistic study

Rodríguez

Nudelman

2013

J of Physical Organic Chem

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The intramolecular carbolithiation‐cyclization‐electrophilic substitution sequence proves to be a promising strategy for synthetic organic chemists. Our current research in this area focuses on the one‐pot halogen/lithium exchange of 2‐bromophenyl‐3‐phenylprop‐2‐enyl ether, followed by intramolecular carbolithiation, and trapping of the new lithiated cyclic intermediate by several electrophiles, affording 3‐substituted 2,3‐dihydrobenzofurans with some diastereoselectivity. Within this context, a study on the product distribution solvent dependence was carried out using different types of solvents, namely: polar coordinating, polar non‐coordinating, and non‐polar solvents. The results show that the coordinating features of the solvent affect specially the carbolithiation step, whereas the halogen/lithium exchange seems to be barely affected. Theoretical calculations were carried out to investigate the unexpected diastereoselectivity of the tandem reaction, where two stereocenters are generated. Insights gained from our mechanistic investigations enabled us to propose an inversion of configuration at the lithiated intermediate prior to the reaction, being the electrophile the likely cause for the observed distereoselectivity. Copyright © 2013 John Wiley & Sons, Ltd.

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“…Another reaction that exhibits some parallels to the TruceSmiles rearrangement is the so-called 62 "Clayden rearrangement" (Scheme 19), a 1,4-aryl migration reaction 63,64 that could be viewed as proceeding through an intermediate that is highly related to a 5-membered spirocyclic Meisenheimer adduct, a hypothesis supported 65,66 by mechanistic studies.…”

Section: Radical Mechanismsmentioning

confidence: 82%

The Truce–Smiles rearrangement and related reactions: a review

2017

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Abstract:The Truce-Smiles rearrangement is an X ¡ C aryl migration reaction that is achieved by an intramolecular nucleophilic aromatic substitution pathway. The reaction exhibits a wide substrate scope with respect to a migrating aryl ring and leaving group, appearing in many different tandem reaction sequences, to achieve a wide variety of product outcomes. We present an extensive survey of reported examples of the Truce-Smiles rearrangement from the chemistry literature (1950s until present) organized by various substrate design variables or aspects of the reaction method. Present deficiencies in our understanding of the reaction are identified with recommendations for future research directions and useful developments in the application of the reaction are celebrated.

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Dearomatization and Aryl Migration in Organolithium Chemistry

Cited by 6 publications

References 70 publications

Alkylation of the K-Region in a Sterically Hindered Pyrene Carboxamide via Directed Reaction with Alkyllithiums under Air

Alkylation of the K-Region in a Sterically Hindered Pyrene Carboxamide via Directed Reaction with Alkyllithiums under Air

Intramolecular carbolithiation‐cyclization‐electrophilic substitution: solvent effect and mechanistic study

The Truce–Smiles rearrangement and related reactions: a review

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