The Halogen/Metal Interconversion and Related Processes (M = Li, Mg)

Panossian, Armen; Leroux, Frédéric R.

doi:10.1002/9781118754887.ch28

Arene Chemistry 2015

DOI: 10.1002/9781118754887.ch28

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The Halogen/Metal Interconversion and Related Processes (M = Li, Mg)

Armen Panossian

Frédéric R. Leroux

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Cited by 5 publications

References 107 publications

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Ein Zugang zum enantiomerenreinen axial chiralen Cyclophan Isoplagiochin D durch atrop‐diastereoselektive Heck‐Kupplung

et al. 2018

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Die Makrocyclisierung ist üblicherweise der Schlüsselschritt in der Synthese von Naturstoffen des Typs Cyclophan. Betrachtet man Cyclophane mit axial chiralen Biaryleinheiten, so ist die Kontrolle der Atropselektivitäthinsichtlich Synthese und biologischen Aktivitäten -wesentlich und herausfordernd. Wirberichten über einen atropselektiven Zugang via Heck-Cyclisierung, der erstmals die Totalsynthese eines enantiomerenreinen makrocyclischen Bis(bibenzyls), hier Isoplagiochin D, erlaubt. Ein enantiomerenreines Sulfinyl-Auxiliar in ortho-Position einer (noch flexiblen) Biarylachse induziert eine atrop-diastereoselektive Heck-Kupplung (bis zu 98 %d e). Der spurlose Charakter des Sulfinyl-Auxiliars ermçglicht anschließend effektiv die Einführung einer Hydroxylgruppe und so die Gewinnung des Zielmoleküls mit ebenfalls 98 %ee.

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Ein Zugang zum enantiomerenreinen axial chiralen Cyclophan Isoplagiochin D durch atrop‐diastereoselektive Heck‐Kupplung

et al. 2018

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Access to the Enantiopure Axially Chiral Cyclophane Isoplagiochin D through Atropo‐diastereoselective Heck Coupling

et al. 2018

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Macrocyclization is typically the key step in the syntheses of cyclophane-type natural products. Considering cyclophanes with axially chiral biaryl moieties, the control of atroposelectivity is essential with biological activity and is synthetically challenging. We report an atroposelective approach involving Heck cyclization, which for the first time enables the total synthesis of an enantiopure macrocyclic bis(bibenzyl), namely isoplagiochin D. An enantiopure sulfinyl auxiliary in the ortho position of a biaryl axis (still flexible) was used to induce an atropo-diastereoselective Heck coupling (up to 98 % de). The traceless character of the sulfinyl auxiliary enables the introduction of a hydroxy group to give the target molecule with 98 % ee as well.

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The Mechanism of Lithium Zincate‐Mediated I/Zn Exchange Revisited: A Computational Microsolvation Approach in THF**

Pierret,

Lefebvre,

Gros

et al. 2023

Eur J Org Chem

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Lithium trialkylzincate‐mediated I/Zn exchange reaction has been revisited computationally through a micro‐solvation approach. A never yet investigated iodoaryl derivative bearing a potential bulky para‐directing group, namely 4‐iodobenzyl mesylate, was considered as a substrate. THF as typical solvent and Et3ZnLi have also been considered for the first time in such a reaction. Three mechanistic pathways have been calculated, including (1) a literature‐inspired pathway with full preservation of the synergic character of the reagent as well as a complementary mesylate group‐directed pathway, (2) a THF‐solvated open complex‐promoted pathway and (3) an anionic pathway. While the anionic pathway appeared to be unlikely, pathway involving a THF‐solvated open zincate complex turned out to be the most energetically favoured. Equivalent thermodynamic profiles were found for both complementary pathways with preservation of the synergic character of the reagent, albeit a slight preference could be attributed to that occurring with initial chelation of Li to the mesylate group (OMs) through micro‐solvation approach. The I/Zn exchange was shown to proceed through a lithium‐assisted aryl shuttle‐like process. The iodoaryl substrate is first converted into ArLi intermediate which in turns reacts with the remaining diorganozinc reagent.

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The Halogen/Metal Interconversion and Related Processes (M = Li, Mg)

Cited by 5 publications

References 107 publications

Ein Zugang zum enantiomerenreinen axial chiralen Cyclophan Isoplagiochin D durch atrop‐diastereoselektive Heck‐Kupplung

Ein Zugang zum enantiomerenreinen axial chiralen Cyclophan Isoplagiochin D durch atrop‐diastereoselektive Heck‐Kupplung

Access to the Enantiopure Axially Chiral Cyclophane Isoplagiochin D through Atropo‐diastereoselective Heck Coupling

The Mechanism of Lithium Zincate‐Mediated I/Zn Exchange Revisited: A Computational Microsolvation Approach in THF**

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