Theoretical Studies of [2,3]-Sigmatropic Rearrangements of Allylic Selenoxides and Selenimides

Bayse, Craig A.; Antony, Sonia

doi:10.3390/molecules14093229

Cited by 5 publications

(1 citation statement)

References 27 publications

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“…35 Our group has also investigated these interactions in selenoxide elimination from Se-substituted selenocysteines, 57 and [2,3]-sigmatropic rearrangements of allylic selenoxides. 58 Before examining the effect of Se ◊ ◊ ◊ N,O interactions upon the GPx-like mechanism in Scheme 1, we briefly discuss the strengths of these interactions for a series of 84 ortho-substituted divalent arylselenium compounds (4-15 where X = Me, SMe, SeMe, CN, SCN, N 3 , Cl, Br, I and OH). Geometries of these species (see Tables S1-S4 in ESI †) were optimized at the DFT(mPW1PW91)/BSI level followed by NBO calculations of the donor-acceptor energy (DE d → a ).…”

Section: Resultsmentioning

confidence: 99%

Tuning the activity of glutathione peroxidase mimics through intramolecular Se⋯N,O interactions: A DFT study incorporating solvent-assisted proton exchange (SAPE)

Bayse

Pavlou

2011

Org. Biomol. Chem.

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Diaryl diselenide mimics of the antioxidant selenoprotein glutathione peroxidase (GPx) often incorporate intramolecular Se···N,O interactions to enhance their GPx-like activity. Although the strength of the interaction is defined by the Lewis basicity of the donating group and the strength of the Se-X bond, there is not a clear relationship between the interaction and the GPx-like activity. Density-functional theory and natural bond orbital (NBO) calculations are used to show the range of Se···N,O interactions for various functional groups. The strongest interactions are found for groups which stabilize the donor-acceptor interaction through aromatic stabilization. The activation barriers for the GPx-like mechanism of activity of several substituted areneselenols are calculated using DFT and solvent-assisted proton exchange (SAPE), a technique that incorporates networks of solvent molecules into the theoretical model to facilitate proton transfer between sites in the reactant and product. DFT-SAPE models show that, in addition to decreasing the barrier to oxidation of the selenol, Se···N,O interactions generally increase the barriers for selenenic acid reduction and selenol regeneration because the Se···N,O interaction must be broken for the reaction to proceed. Calculated activation barriers for the rate-determining step are consistent with the relative experimental GPx-like activities of a series of diaryl diselenides.

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Section: Resultsmentioning

confidence: 99%

Tuning the activity of glutathione peroxidase mimics through intramolecular Se⋯N,O interactions: A DFT study incorporating solvent-assisted proton exchange (SAPE)

Bayse

Pavlou

2011

Org. Biomol. Chem.

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Theoretical Aspects of Organoselenium Chemistry

Sunoj

2011

Patai's Chemistry of Functional Groups

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The chapter offers an overview of the applications of theoretical methods in the area of organoselenium chemistry. In recent years, the availability of reliable basis sets and computational methods, especially the emergence of density functional methods, have enabled studies on increasingly complex chemical problems. A plethora of such problems in organoselenium chemistry and interesting insights on structure, properties, and reactions derived by using computational methods constitute the contents of this chapter. The types of situations described range from exotic briefly lived intermediates to structural and electronic features of stable and crystalline molecules. Properties such as nuclear magnetic resonance chemical shift and the comparison between computed and experimental quantities have been provided extensively. A number of reactions of selenium compounds with emphasis on biologically significant reactions have been highlighted. In particular, computational studies on glutathione peroxidate activity of selenium compounds have been elaborated. The electronic origins of inter‐ and intra‐molecular nonbonding interactions in organoselenium compounds and an illustration of how theoretical methods have been vital in quantifying such weak interactions have been provided.

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Organoselenium and Organotellurium Oxidation and Reduction

Młochowski

Lisiak

Wójtowicz‐Młochowska

2011

Patai's Chemistry of Functional Groups

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Oxygenated and reduced selenium and tellurium compounds, particularly thoese of practical importance have been extensively investigated especially during the last few decades. Selenium(IV) oxide, selenoxides, selenones, seleninic and peroxyseleninic acids, selenenamides and seleninamides are involved in oxyfunctionalization of unsaturated hydrocarbons, their derivatives, alkylarenes, sulfides and amines, carbon‐oxygen and carbon‐carbon bond cleavage, ring closure and ring transformations, syn ‐elimination, sigmatropic [2,3]‐rearrangement and other, chemo‐ regio‐ and stereocontrolled reactions. The chemistry of oxygenated tellurium compounds has been less extensively explored than their selenium counterparts;, nevertheless some of them have been successfully used for oxyfunctionalization of different groups of organic compounds while telluroxide elimination has gained more attention in the last years becoming a well‐established method for the synthesis of olefins. Hydrogen selenide and telluride, alkali selenides and tellurides, selenoles and telluroles are the most common reduced derivative of these elements. Their properties are expressed in many reactions such as reduction and deoxygenation of different groups of organic compounds alkenes, alkynes, ethers, carbonyl compounds, esters, lactones, oxiranes, nitrogen, sulfur and halogen compounds, as well as dealkylation of tertiary amines. The method for preparation of the different oxygenated and reduced selenium and tellurium compounds are described, their reactions are reviewed, their usefulness in synthesis is indicated and more representative mechanisms are discussed.

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Theoretical Studies of [2,3]-Sigmatropic Rearrangements of Allylic Selenoxides and Selenimides

Cited by 5 publications

References 27 publications

Tuning the activity of glutathione peroxidase mimics through intramolecular Se⋯N,O interactions: A DFT study incorporating solvent-assisted proton exchange (SAPE)

Tuning the activity of glutathione peroxidase mimics through intramolecular Se⋯N,O interactions: A DFT study incorporating solvent-assisted proton exchange (SAPE)

Theoretical Aspects of Organoselenium Chemistry

Organoselenium and Organotellurium Oxidation and Reduction

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