Disproportionierung der Sulfinsäuren und die Struktur der Sulfinsäureanhydride

Bredereck, Hellmut; Wagner, Adolf; Beck, Erich; Herlinger, Heinz; Kottenhahn, K.‐G.

doi:10.1002/ange.19580700904

Cited by 23 publications

(4 citation statements)

References 2 publications

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“…As these radicals are in an electronic doublet state, they can then quickly react with molecular oxygen, which is in the triplet state (Figure ). The intermediate peroxide species quickly rearranges under formation of a sulfinic acid, which in turn is not stable and either disproportionates , or reacts with another oxygen molecule to form the thermodynamically most favored sulfonate, which therefore is the only or strongly dominant product species observable in the S 2p XP spectra.…”

Section: Discussionmentioning

confidence: 99%

Modification of Alkanethiolate Self-Assembled Monolayers by Ultraviolet Light: The Effect of Wavelength

2021

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The effect of the wavelength upon the modification of the archetypical nonsubstituted alkanethiolate (AT) selfassembled monolayers (SAMs) on Au(111) by ultraviolet (UV) light was investigated. As a test system, the dodecanethiolate monolayer was selected, while the wavelength of the UV light was varied in two steps from 254 to 375 nm, which is a relevant range for a variety of inexpensive UV sources as well as custom-made and commercial lithography setups. The absolute cross sections of the most prominent and application-relevant UV-induced processes, above all photooxidation of the thiolate anchoring groups to sulfonates, were determined. They were found to decrease exponentially with increasing wavelength, with an effective "wavelength attenuation parameter" of ∼24 nm. This behavior was rationalized within a model assuming the primary role of UV-induced hot electrons, originating from the substrate and triggering an excitation and subsequent oxidation of the sulfur atoms by their reaction with oxygen molecules, penetrating to the SAM−substrate interface across the SAM matrix. The observed behavior and the absolute values of the photooxidation cross sections represent a useful "tool" for the estimation of a proper dose or dose range in the applications involving modification of AT SAMs and thiolate SAMs in general by UV light.

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Section: Discussionmentioning

confidence: 99%

Modification of Alkanethiolate Self-Assembled Monolayers by Ultraviolet Light: The Effect of Wavelength

2021

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“…1B), which are high-valent analogues of disul des, have been known for over a century 26 . However, their structure and reactivity has only been sporadically investigated [27][28][29][30] ; the perception that sul nyl sulfones are unstable, hard-to-handle materials, along with a lack of reliable methods for their synthesis, has deterred research and restricted their occasional use as electrophilic sulfur sources [31][32][33] . A single report suggested that their thermal decomposition might proceed via homolytic ssion, generating two distinct sulfur-centered radicals-a sul nyl radical and a sulfonyl radical 34 .…”

Section: Main Textmentioning

confidence: 99%

Synthetic exploration of sulfinyl radicals using sulfinyl sulfones

Wang

Zhang

Zhao

et al. 2021

Preprint

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Sulfinyl radicals – one of the fundamental classes of S-centered radicals – have eluded synthetic application in organic chemistry for over 60 years, despite their potential to assemble valuable sulfoxide compounds. Here we report the successful generation and use of sulfinyl radicals in a dual radical addition / radical coupling with unsaturated hydrocarbons, where readily-accessed sulfinyl sulfones serve as the sulfinyl radical precursor. The strategy provides an entry to a variety of previously inaccessible linear and cyclic disulfurized adducts in a single step, and demonstrates excellent tolerance to an extensive range of hydrocarbons and functional groups. Experimental and theoretical mechanistic investigations suggest that these reactions proceed through sequential sulfonyl and sulfinyl radical addition.

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“…Sulfinyl sulfones, as more-than-100-year-history typically multioxidative sulfides, 5 have both had the distinctive features of sulfone and sulfoxide. The development of sulfinyl sulfones was extremely slow before 2021, mainly focusing on the characterization of their physical and chemical properties; however, synthetic research was sporadically investigated 6 due to the perception of their instability and a lack of reliable synthesis methods, which has restricted their occasional use as electrophilic sulfur sources 7 (Scheme 1A). Notably, as a pioneer in this field, in 2021 the Bi group 8a first reported the successful in situ generation and use of sulfinyl sulfones as distinctive and powerful bifunctional reagents in a dual radical addition/radical coupling with unsaturated hydrocarbons to provide an entry to a variety of previously inaccessible linear and cyclic disulfurized adducts.…”

Section: Introductionmentioning

confidence: 99%

Exploration on Metal-Catalytic Conversion of Sulfinyl Sulfones

Li,

Liu,

Shan

et al. 2023

ACS Catal.

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The utilization of sulfinyl sulfones in transitionmetal-catalyzed synthetic chemistry has rarely been investigated.Here we report the design and utilization of nickel-catalytic conversion of in situ-generated redox-active sulfinyl sulfones for reductive coupling with a wide variety of organic halides by the dual-role nickel catalyst and dual-role reductant Zn. Mechanistic studies disclose that the key design of such a reaction is the employment of redox-active sulfinyl sulfones, enabling the in situ generation of electrophilic sulfur reagents through zinc-induced reduction facilitated by the nickel catalyst. This strategy demonstrates good tolerance for a wide range of organic halides and functional groups. Furthermore, this method extends to meta-substituted functional diaryl sulfides, enabling the modification of complex bioactive molecules and the synthesis of thioether-containing drugs.

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Disproportionierung der Sulfinsäuren und die Struktur der Sulfinsäureanhydride

Cited by 23 publications

References 2 publications

Modification of Alkanethiolate Self-Assembled Monolayers by Ultraviolet Light: The Effect of Wavelength

Modification of Alkanethiolate Self-Assembled Monolayers by Ultraviolet Light: The Effect of Wavelength

Synthetic exploration of sulfinyl radicals using sulfinyl sulfones

Exploration on Metal-Catalytic Conversion of Sulfinyl Sulfones

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