Recent Advances in the Substitution Reactions of Triorganylstannyl Ions with Aromatic Compounds by the SRN1 Mechanism. Synthetic Applications

Eduardo F Córsico,Al Postigo,Roberto A Rossi

doi:10.3390/50901068

Eduardo F Córsico, Al Postigo + Show 1 more

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https://doi.org/10.3390/50901068

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Abstract

A review on the reactions of triorganyl stannyl ions with haloarenes is presented. Emphasis on the synthetic applications of the resulting triorganyl stannyl aryl compounds is made, with their inherent potential to build large molecules through the SRN1 sequence, i.e. ArX→ArSnR3→ArAr, which can be iteratively repeated when appropriately substituted substrates are chosen.

Highlights

The reaction of triorganostannyl ions as nucleophiles with haloarenes has long been known, and the products obtained depend on the nucleophile, solvent, and on the reaction conditions
In this review we present the results of the reactions of organotin nucleophiles with aryl halides by the SRN1 mechanism and their synthetic applications
A second Pd(0)-catalyzed reaction with 1-iodonaphthalene renders product 38 in 93% yield. All these results indicate that the SRN1 mechanism is an excellent method to obtain stannanes by the photostimulated reactions of mono, di- and trichloro arenes with Me3Sn- in liquid ammonia

Summary

Introduction

The reaction of triorganostannyl ions as nucleophiles with haloarenes has long been known, and the products obtained depend on the nucleophile, solvent, and on the reaction conditions. The reaction of o-dibromobenzene with NaSnMe3 affords the disubstitution product o-bis(trimethylstannyl) benzene in 42% yield. In this reaction, the intermediate o-bromophenyl anion, can decompose into benzyne, which can be trapped with furan to render the corresponding Diels-. When radical traps are added, cine substitution products increase in yields, and in the presence of Li metal, the yields of ipso products are enhanced According to these results, the reaction should proceed, at least in part, by a radical mechanism [3]. We have described the photostimulated reactions of haloarenes with triorganylstannyl ions by the SRN1 mechanism These reactions afford good to excellent yields of the nucleophilic substitution products.

Me3Sn- Ions as Nucleophile

Ph3Sn- Ions as Nucleophile

Other Tin-derived Nucleophiles

Synthetic Applications

Findings

Conclusions and Summary Remarks