smiles rearrangement
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Synthesis ◽  
2021 ◽  
Author(s):  
David Whalley ◽  
Michael Greaney

The Smiles rearrangement has undergone a renaissance in recent years providing new avenues for non-canonical arylation techniques in both the radical and polar regimes. This Short Review will discuss recent applications of the reaction (from 2017 onwards), including its relevance to areas such as heterocycle synthesis, functionalisation of alkenes and alkynes as well as glimpses at new directions for the field.


Molecules ◽  
2021 ◽  
Vol 26 (22) ◽  
pp. 6879
Author(s):  
Krystian Kolodziejczak ◽  
Alexander J. Stewart ◽  
Tell Tuttle ◽  
John A. Murphy

Rearrangements of o-tolyl aryl ethers, amines, and sulfides with the Grubbs–Stoltz reagent (Et3SiH + KOtBu) were recently announced, in which the ethers were converted to o-hydroxydiarylmethanes, while the (o-tol)(Ar)NH amines were transformed into dihydroacridines. Radical mechanisms were proposed, based on prior evidence for triethylsilyl radicals in this reagent system. A detailed computational investigation of the rearrangements of the aryl tolyl ethers now instead supports an anionic Truce–Smiles rearrangement, where the initial benzyl anion can be formed by either of two pathways: (i) direct deprotonation of the tolyl methyl group under basic conditions or (ii) electron transfer to an initially formed benzyl radical. By contrast, the rearrangements of o-tolyl aryl amines depend on the nature of the amine. Secondary amines undergo deprotonation of the N-H followed by a radical rearrangement, to form dihydroacridines, while tertiary amines form both dihydroacridines and diarylmethanes through radical and/or anionic pathways. Overall, this study highlights the competition between the reactive intermediates formed by the Et3SiH/KOtBu system.


2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Fengjuan Chen ◽  
Youxiang Shao ◽  
Mengke Li ◽  
Can Yang ◽  
Shi-Jian Su ◽  
...  

AbstractSila-molecules have recently attracted attention due to their promising applications in medical and industrial fields. Compared with all-carbon parent compounds, the different covalent radius and electronegativity of silicon from carbon generally endow the corresponding sila-analogs with unique biological activity and physicochemical properties. Vinylsilanes feature both silyl-hyperconjugation effect and versatile reactivities, developing vinylsilane-based Smiles rearrangement will therefore provide an efficient platform to assemble complex silacycles. Here we report a practical Ir(III)-catalyzed cycloaromatization of ortho-alkynylaryl vinylsilanes with arylsulfonyl azides for delivering naphthyl-fused benzosiloles under visible-light photoredox conditions. The combination of experiments and density functional theory (DFT) energy profiles reveals the reaction mechanism involving α-silyl radical Smiles rearrangement.


2021 ◽  
Author(s):  
Roman Abrams ◽  
Mehul H. Jesani ◽  
Alex Browning ◽  
Jonathan Clayden

2021 ◽  
Vol 13 (4) ◽  
pp. 327-334 ◽  
Author(s):  
Cédric Hervieu ◽  
Mariia S. Kirillova ◽  
Tatiana Suárez ◽  
Marco Müller ◽  
Estíbaliz Merino ◽  
...  

2021 ◽  
pp. 130156
Author(s):  
Abdullah Mohammed Al-Majid ◽  
Saied M. Soliman ◽  
Hazem A. Ghabbour ◽  
M. Ali ◽  
Mohammad Shahidul Islam ◽  
...  

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