The stereochemistry of the formation of Δ3-1,3,4-thiadiazoline-1-oxides and episulfoxides from sulfines and 2-diazopropane

Thijs, L.; Wagenaar, Anno; Rens, Eva; Zwanenburg, B.

doi:10.1016/s0040-4039(01)86978-1

Cited by 21 publications

(2 citation statements)

References 3 publications

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“…This activity is different to that of diarylsulfines, and 2 equiv. [125] Scheme 56. [124] This product is formed by the rearrangement and cyclisation of the intermediate carbanion generated by the nucleophilic attack.…”

Section: Thiophilic Nucleophilic Attackmentioning

confidence: 99%

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Generation, Reactivity and Uses of Sulfines in Organic Synthesis

et al. 2016

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This review focuses on the synthesis and reactivity of thioketone S‐oxides (sulfines). Sulfines have been long established as being reactive intermediates of high interest and with potential for wide application in organic synthesis. The review will cover many aspects of sulfines: the first section looks at the different routes to the synthesis of these compounds with a detailed look at more recently developed routes; the second section details the scope of reactivity of these types of compounds and how they are useful in synthetic organic chemistry with a particular look at cycloaddition and nucleophilic addition reactions.

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Section: Thiophilic Nucleophilic Attackmentioning

confidence: 99%

“…The rearrangement of the zwitterionic species and loss of nitrogen from the intermediate 124 lead to a nonstereospecific cyclisation and formation of episulfoxides, in place of the expected five-membered cycloadduct. [125] Eur. J.…”

Section: Thiophilic Nucleophilic Attackmentioning

confidence: 99%

Generation, Reactivity and Uses of Sulfines in Organic Synthesis

et al. 2016

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Twofold Extrusion Reactions

Guziec

2012

Organic Reactions

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Twofold extrusion reactions are chemical transformations in which two small inorganic molecules or atoms connecting carbon or nitrogen atoms are lost, generating the corresponding carbon‐carbon or carbon‐nitrogen double bonds. These reactions are particularly useful for the preparation of sterically hindered alkenes and imines. The inorganic species liberated in twofold extrusion reactions can be molecular nitrogen, sulfur, selenium, tellurium, sulfur dioxide, sulfur monoxide, carbon dioxide or carbon monoxide. The most common precursors for twofold extrusion reactions are 1,3,4‐thiadiazolines, which thermally extrude molecular nitrogen affording thiiranes. These thiiranes can be readily desulfurized to afford the corresponding alkenes using tertiary phosphines. The corresponding 1,3,4‐selenadiazolines thermally extrude both molecular nitrogen and atomic selenium directly affording alkenes. Alkenes can also be prepared by formal extrusions of molecular nitrogen plus sulfur dioxide or sulfur monoxide. Extremely sterically hindered imines can be prepared by extrusions of molecular nitrogen and sulfur or selenium from in situ generated heterocyclic precursors. Other less common twofold extrusion reactions are also reported. The detailed preparations of the required precursors for the twofold extrusion reactions as well as the mechanisms of these extrusion processes are discussed in this chapter. The utility of twofold extrusion reactions in the preparations of ‘molecular rotors’ and other extremely sterically hindered alkenes is presented. The steric limitations of the twofold extrusion reactions are discussed along with comparisons of these reactions with other alkene‐ and imine‐forming synthetic methods. The Tabular Survey covers material through the end of 2009.

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