A DFT examination of the role of proximal boron functionalities in the <i>S</i>-alkylation of sulfenic acid anions

Durant, Andrew G.; Nicol, Eric; McInnes, Brandon M.; Schwan, Adrian L.

doi:10.1039/d1ob02083h

Cited by 3 publications

(1 citation statement)

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“…The potential problem of spin contamination for 6 was examined using the T1 diagnostic of Lee and Taylor (43). Finally, DFT calculations are known to reproduce experimental disulfide and sulfur‐oxygen intermediate structural features based on comparison with experimental structures (44–49). DFT methods such as M06‐2X also perform well with sulfur–sulfur long pair interactions and in computing 1 O 2 reactions leading to peroxy species (5,50).…”

Section: Theoretical Sectionmentioning

confidence: 99%

Singlet Oxygen's Potential Role as aNonoxidativeFacilitator of Disulfide S–S Bond Rotation^†

Turque

O'Connor

Greer

2022

Photochem & Photobiology

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The role of singlet oxygen potentially mediating increased conformational flexibility of a disulfide was investigated. Density functional theory (DFT) calculations indicate that the singlet oxygenation of 1,2‐dimethyldisulfane produces a peroxy intermediate. This intermediate adopts a structure with a longer S–S bond distance and a more planar torsional angle θ (C–S–S–C) compared with the nonoxygenated 1,2‐dimethyldisulfane. The lengthened S–S bond enables a facile rotation about the torsional angle in the semicircle region 0° < θ < 210°, that is ~5 kcal mol−1 lower in energy than the disulfane. The peroxy intermediate bears nO → σS–S and nO → σ*S–S interactions that stabilize the S–O bond but destabilize the S–S bond, which contrasts with stabilizing nS → σ*S–S hyperconjugative effects in the disulfane S–S bond. Subsequent departure of O2 from the disulfane peroxy intermediate is reminiscent of peroxy intermediates which also expel O2, yet facilitate cis‐trans isomerizations of stilbenes, hexadienes, cyanines, and carotenes. “Non‐oxidative” 1O2 interactions with a variety of bond types are currently underappreciated. We hope to raise awareness of how these interactions can help elucidate the origins of molecular twisting.

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Section: Theoretical Sectionmentioning

confidence: 99%

Singlet Oxygen's Potential Role as aNonoxidativeFacilitator of Disulfide S–S Bond Rotation^†

Turque

O'Connor

Greer

2022

Photochem & Photobiology

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Proximal interactions can direct selective sulfenate alkylation chemistry

Schwan

Nicol

Durant

2023

Phosphorus, Sulfur, and Silicon and the Related Elements

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The generation and reactions of sulfenate anions. An update

Riddell

Smith

Schwan

2022

Journal of Sulfur Chemistry

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A DFT examination of the role of proximal boron functionalities in the S-alkylation of sulfenic acid anions

Abstract: DFT modelling predicts proximal boron groups can accelerate sulfenate alkylation reactions, depending on boron substituents and boron distance from the reaction site.

Cited by 3 publications

References 44 publications

Singlet Oxygen's Potential Role as aNonoxidativeFacilitator of Disulfide S–S Bond Rotation^†

Singlet Oxygen's Potential Role as aNonoxidativeFacilitator of Disulfide S–S Bond Rotation^†

Proximal interactions can direct selective sulfenate alkylation chemistry

The generation and reactions of sulfenate anions. An update

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A DFT examination of the role of proximal boron functionalities in the S-alkylation of sulfenic acid anions

Abstract: DFT modelling predicts proximal boron groups can accelerate sulfenate alkylation reactions, depending on boron substituents and boron distance from the reaction site.

Cited by 3 publications

References 44 publications

Singlet Oxygen's Potential Role as aNonoxidativeFacilitator of Disulfide S–S Bond Rotation†

Singlet Oxygen's Potential Role as aNonoxidativeFacilitator of Disulfide S–S Bond Rotation†

Proximal interactions can direct selective sulfenate alkylation chemistry

The generation and reactions of sulfenate anions. An update

Contact Info

Product

Resources

About

Singlet Oxygen's Potential Role as aNonoxidativeFacilitator of Disulfide S–S Bond Rotation^†

Singlet Oxygen's Potential Role as aNonoxidativeFacilitator of Disulfide S–S Bond Rotation^†