Reductive Cleavage of the Se–Se Bond in the Presence of a Zn/AlCl<sub>3</sub> System: Synthesis of Selenol Esters

Movassagh, Barahman; Shamsipoor, Mojgan; Joshaghani, Mohammad

doi:10.3184/030823404323000549

Cited by 8 publications

(2 citation statements)

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“…[11][12][13][14] They were also used as a precursors in the synthesis of vinyl compounds, 15 in the formation of C-peptide bonds, [16][17][18] and the synthesis of some natural occurring compounds, [19][20][21][22][23] besides having proven antioxidant properties. 24 Various methods have been described for the synthesis of selenol esters, for example, by the condensation of selenolate anions 25 or radicals 26 with carbonyl compounds, such as aldehydes, 27,28 anhydrides 26,29-34 acyl chlorides [29][30][31][32][33][34] or starting from chalcogen acetylenes 35 and aryl iodides. 36 Generally, these methods have limitations related to metal-catalyzed synthesis, 37 high temperatures and volatile solvents 29 and long reaction times.…”

Section: Introductionmentioning

confidence: 99%

Rongalite®/PEG-400 as reducing system in the synthesis of new glycerol-derived selenol esters using anhydrides and bis-(2,2-dimethyl-1,3-dioxolanylmethyl)diselenide as substrates

Perin¹,

Silveira²,

Barcellos³

et al. 2016

Arkivoc

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Section: Introductionmentioning

confidence: 99%

Rongalite®/PEG-400 as reducing system in the synthesis of new glycerol-derived selenol esters using anhydrides and bis-(2,2-dimethyl-1,3-dioxolanylmethyl)diselenide as substrates

Perin¹,

Silveira²,

Barcellos³

et al. 2016

Arkivoc

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“…Diselenide compounds are of special interest within the huge family of selenium derivatives for their applications in organic synthesis − and as therapeutic drugs. , Besides, they are also found in proteins as diselenide bridges, in a similar fashion to sulfur-containing peptides. Diselenides are well-known for their high antioxidant activity, − which is actually higher than that of disulfides, so the study of their reductive cleavage has attracted considerable attention. − However, there is not enough information to fully understand the mechanism of this process. In the present contribution we would like to shed some light on this open question by modeling the reductive cleavage of diselenides with the electron-capture dissociation (ECD) reaction, a process largely investigated for disulfides − but which has not received such attention in the case of diselenides.…”

Section: Introductionmentioning

confidence: 99%

Electron Attachment to Diselenides Revisited: Se–Se Bond Cleavage Is Neither Adiabatic nor the Most Favorable Process

Gámez

Yáñez

2011

J. Chem. Theory Comput.

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Up to now it has been generally assumed that the electron capture on diselenides XSeSeX' produces a fragmentation of the Se-Se bond. However, our high-level ab initio calculations indicate that this is the case only when the substituents X and X' attached to the diselenide bridge have low electronegativity. Also importantly, even when the two substituents are of similar electronegativity, the Se-Se bond cleavage rarely is an adiabatic process. For low-electronegative X substituents, the extra electron is placed in the σ*(Se-Se) antibonding orbital, and the cleavage of the Se-Se bond is the most favorable process. However, the mechanism of this bond breaking is more intricate than previously assumed, and for asymmetric derivatives it proceeds through a conical intersection (CI). These findings emphasize the importance of using accurate ab initio calculations, rather than the usually employed density functional theory approaches, when dealing with reactions in biochemistry and organometallic chemistry, because the characterization of a CI requires the use of multireference methods to account for the mixing of states. When X is highly electronegative, the σ*(Se-X) antibonding orbital becomes highly stabilized with respect to the σ*(Se-Se) strongly favoring the cleavage of the Se-X bond, whereas the Se-Se remains practically unperturbed. Finally, when comparing the present results on diselenides with those of the disulfide analogues, it is apparent that the activation barriers and the final products of the different unimolecular reactions are higher in energy for the diselenides, in spite of the higher antioxidant strength of diselenides. This seems to indicate that the electron detachment process, less favorable for diselenides than for disulfides, competes with the electron-capture dissociation process and therefore should also be considered to explain the different antioxidant ability of these compounds.

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Organoselenium Chemistry

Singh

Wirth

2018

Encyclopedia of Inorganic and Bioinorganic Chemistry

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Organoselenium chemistry has been established as a valuable research area in synthetic and medicinal chemistry. After the discovery of the selenoxide elimination reaction in the early 1970s, organoselenium reagents achieved great success in organic synthesis including asymmetric synthesis. More commonly, synthetic transformations such as selenenylation, selenocyclization, and 2,3‐sigmatropic rearrangements have been successfully achieved using these reagents under mild reaction conditions. The application of these reagents in catalysis makes them more suitable reagents in organic synthesis. Several books, book chapters, and review articles have been published to explain the utility of organoselenium reagents in synthesis. This article highlights the application of organoselenium reagents in organic synthesis including asymmetric synthesis.

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Reductive Cleavage of the Se–Se Bond in the Presence of a Zn/AlCl₃ System: Synthesis of Selenol Esters

Abstract: Selenol esters were prepared in good yields by reacting diselenides with carboxylic acid anhydrides in dry acetonitrile in the presence of a Zn/AlCl 3 system.

Cited by 8 publications

References 47 publications

Rongalite®/PEG-400 as reducing system in the synthesis of new glycerol-derived selenol esters using anhydrides and bis-(2,2-dimethyl-1,3-dioxolanylmethyl)diselenide as substrates

Rongalite®/PEG-400 as reducing system in the synthesis of new glycerol-derived selenol esters using anhydrides and bis-(2,2-dimethyl-1,3-dioxolanylmethyl)diselenide as substrates

Electron Attachment to Diselenides Revisited: Se–Se Bond Cleavage Is Neither Adiabatic nor the Most Favorable Process

Organoselenium Chemistry

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Reductive Cleavage of the Se–Se Bond in the Presence of a Zn/AlCl3 System: Synthesis of Selenol Esters

Abstract: Selenol esters were prepared in good yields by reacting diselenides with carboxylic acid anhydrides in dry acetonitrile in the presence of a Zn/AlCl 3 system.

Cited by 8 publications

References 47 publications

Rongalite®/PEG-400 as reducing system in the synthesis of new glycerol-derived selenol esters using anhydrides and bis-(2,2-dimethyl-1,3-dioxolanylmethyl)diselenide as substrates

Rongalite®/PEG-400 as reducing system in the synthesis of new glycerol-derived selenol esters using anhydrides and bis-(2,2-dimethyl-1,3-dioxolanylmethyl)diselenide as substrates

Electron Attachment to Diselenides Revisited: Se–Se Bond Cleavage Is Neither Adiabatic nor the Most Favorable Process

Organoselenium Chemistry

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Reductive Cleavage of the Se–Se Bond in the Presence of a Zn/AlCl₃ System: Synthesis of Selenol Esters