Selenium and Tellurium Complexes in Organic Synthesis

Santi, Claudio; Scimmi, Cecilia

doi:10.1016/b978-0-12-820206-7.00082-2

Cited by 4 publications

(5 citation statements)

References 103 publications

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“…18,[33][34][35][36][37][38][39][40] The arylation of SeCNby 1 should lead to equimolecular amounts of 2,4,6-trimethoxyphenyliodide and its occurrence decreases AE of the overall process (Figure 2-A). Considering the conventional reactivity mode of arylselenocyanates, namely their ability to generate the electrophilic ArSe + species, [45][46][47] we assumed that the reaction between in situ generated PhSeCN (an ArSe + synthon) with TMP-I (a TMPsynthon) could accomplish the diarylated selenides. These transformations have been previously observed on the arylselenation of electron-rich arenes.…”

Section: Resultsmentioning

confidence: 99%

Metal-free and Atom-efficient Protocol for Diarylation of Selenocyanate by Diaryliodonium Salts

Radzhabov

Soldatova

Ivanov

et al. 2023

Preprint

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The rational search for the efficient protocols for atom-efficient arylation utilizing iodonium salts is the genuine need for the sustainability and green chemistry. We developed a novel approach toward metal-free diarylation of selenocyanate using trimethoxyphenyl-substituted iodonium salts with the formation of appropriate diarylselenides. The suggested procedure allows the preparation of a series of diarylselenides without isolation and purification of intermediate products in two-step one-pot sequence.

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Section: Resultsmentioning

confidence: 99%

Metal-free and Atom-efficient Protocol for Diarylation of Selenocyanate by Diaryliodonium Salts

Radzhabov

Soldatova

Ivanov

et al. 2023

Preprint

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“…2A). Considering the conventional reactivity mode of arylselenocyanates, namely their ability to generate the electrophilic ArSe + species, [43][44][45] we assumed that the reaction between in situ generated PhSeCN (an ArSe + synthon) and TMP-I (a TMP − synthon) could achieve…”

Section: Resultsmentioning

confidence: 99%

“…2A). Considering the conventional reactivity mode of arylselenocyanates, namely their ability to generate the electrophilic ArSe + species, 43–45 we assumed that the reaction between in situ generated PhSeCN (an ArSe + synthon) and TMP-I (a TMP − synthon) could achieve the diarylated selenides. These transformations have been previously observed in the arylselenation of electron-rich arenes.…”

Section: Resultsmentioning

confidence: 99%

Metal-free and atom-efficient protocol for diarylation of selenocyanate by diaryliodonium salts

et al. 2023

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“…The various approaches used for selenation of aromatic compounds include directed lithiation [14,15], copper-catalyzed selenation [16][17][18], and aromatic nucleophilic substitution reactions [19][20][21][22]. Electrophilic selenium reagents (e.g., phenylselenenyl bromide) have often been used in oxyselenenylation of olefins, which follows an electrophilic addition mechanism [23][24][25]. However, such reagents are rarely used for electrophilic substitution of ar-Scheme 1: Reported synthetic methods for the selenation of aromatic compounds.…”

Section: Introductionmentioning

confidence: 99%

Competing electrophilic substitution and oxidative polymerization of arylamines with selenium dioxide

Selladurai,

Karuthapandi

2024

Beilstein J. Org. Chem.

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This article describes the detailed analysis of the reaction between arylamines, such as aniline, o-anisidine, and methyl anthranilate, with selenium dioxide in acetonitrile. A systematic analysis of the reaction products with the help of 77Se NMR and single-crystal X-ray crystallography revealed that the reaction progress follows three major reaction pathways, electrophilic selenation, oxidative polymerization, and solvent oxidation. For aniline and o-anisidine, predominant oxidative polymerization occurred, leading to the formation of the respective polyaniline polymers as major products. For methyl anthranilate, the oxidative polymerization was suppressed due to the delocalization of amine lone pair electrons over the adjacent carboxylate function, which prompted the selenation pathway, leading to the formation of two of the isomeric diorganyl selenides of methyl anthranilate. The diaryl selenides were structurally characterized using single-crystal X-ray diffraction. Density functional theory calculations suggest that the highest occupied molecular orbital of methyl anthranilate was deeply buried, which suppressed the oxidative polymerization pathway. Due to solvent oxidation, oxamide formation was also noticed to a considerable extent. This study provides that utmost care must be exercised while using SeO2 as an electrophile source in aromatic electrophilic substitution reactions.

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Selenium and Tellurium Complexes in Organic Synthesis

Cited by 4 publications

References 103 publications

Metal-free and Atom-efficient Protocol for Diarylation of Selenocyanate by Diaryliodonium Salts

Metal-free and Atom-efficient Protocol for Diarylation of Selenocyanate by Diaryliodonium Salts

Metal-free and atom-efficient protocol for diarylation of selenocyanate by diaryliodonium salts

Competing electrophilic substitution and oxidative polymerization of arylamines with selenium dioxide

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