Bis(trimethylsilyl)selenide in the Selective Synthesis of β‐Hydroxy, β‐Mercapto, and β‐Amino Diorganyl Diselenides and Selenides Through Ring Opening of Strained Heterocycles

Abstract

A novel approach to the synthesis of β-substituted dialkyl diselenides and selenides is described through reaction of bis(trimethylsilyl)selenide with epoxides, thiiranes, and aziridines catalyzed by tetrabutylammonium fluoride. Selective formation of a wide variety of β-hydroxy, β-mercapto, and β-amino diselenides and selenides is achieved by controlling the reaction conditions in the regioselective attack of the silyl

Towards New Catalytic Antioxidants: A Simple and Mild Synthesis of Selenenylsulfides

“…Aryl selenols 1a-d [32], alkyl selenol 1e [31], and N-thiophthalimides 2 [43][44][45][46][47][48] were prepared according to reported procedures. Spectroscopic data of diselenides 4a-e [26,49] and disulfides 5a-h [30] matched those previously reported in the literature. 1 H and 13 C NMR spectra were recorded in CDCl3 or C6D6 with a Varian Mercury Plus instrument or with a Varian INOVA instrument at 400 and 100 MHz, respectively.…”

“…. Het (N, O) interactions [23].Owing to the interest in these selenium containing compounds, the search for novel procedures to prepare small molecules containing the Se-S unit is of great interest.Our long-dated interest in the chemistry of silyl chalcogenides allowed to disclose novel procedures to access a plethora of sulfur and selenium containing molecules exploiting the nucleophilic behaviour of the chalcogen atom towards various electrophiles [24][25][26][27][28][29]. Recently we reported the reaction of bis(trimethylsilyl)selenide (HMDSS) with N-thiophtalimides as a mild, general metal free procedure for the synthesis of variously substituted disulfides [30].Indeed, despite the interest in the reactivity of selenols as nucleophilic selenium transfer reagents, their use has been critically limited by their instability.…”

“…Our long-dated interest in the chemistry of silyl chalcogenides allowed to disclose novel procedures to access a plethora of sulfur and selenium containing molecules exploiting the nucleophilic behaviour of the chalcogen atom towards various electrophiles [24][25][26][27][28][29]. Recently we reported the reaction of bis(trimethylsilyl)selenide (HMDSS) with N-thiophtalimides as a mild, general metal free procedure for the synthesis of variously substituted disulfides [30].…”

Ring opening reactions of heterocycles with selenium and tellurium nucleophiles

“…Epoxides, aziridines, and thiiranes could be selectively converted into the corresponding β-hydroxy-, β-amino-, and β-mercaptoselenides (37-39) or diselenides (40)(41)(42) just tuning the amount of (Me 3 Si) 2 Se. 53 Indeed, selenides were the exclusive reaction products observed when using an excess of the electrophile (ca. 2.0 eq.)…”

A Straightforward Access to Stable β‐Functionalized Alkyl Selenols

“…On the basis of our foregoing results to synthesize selenides and diselenides, the reaction of epoxides with HMDSS 1 was carefully re‐examined in order to search for the suitable way to isolate β‐hydroxyselenols. A systematic investigation was undertaken and a reaction screening was carried out treating 2‐[(allyloxy)‐methyl]oxirane 2 a with HMDSS under different experimental conditions by varying the temperature, the amount of catalyst and the reaction time.…”