Generation and [2+3] Cycloadditions of a Sulfonylated Thiocarbonyl S-Methanide

The unexpected 1,3‐benzodithiine derivatives 5b,c were obtained from the reactions of trimethylsilyldiazomethane 2 with C‐sulfonyldithioformates, bearing pentachlorophenylthio group, 1b,c via unprecedented cyclization of the transient thiocarbonyl ylides 4b,c. While the corresponding reaction with C‐sulfonyldithioformates, bearing phenylthio group, afforded 5a via [2 + 3]‐cycloadditive dimerization of a transient thiocarbonyl ylides 4a. Under the same reaction condition, C‐sulfonyldithioformates 1d–f react with diazomethane and/or phenyldiazomethane to afford the unsymmetrical 1,3‐dithiolane 7d,e and thiirane 8e,f derivatives, respectively. © 2007 Wiley Periodicals, Inc. Heteroatom Chem 18:28–33, 2007; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20246

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Generation and cyclization of thiocarbonyl S‐ylides by reaction of diazocompounds with C‐sulfonyldithioformates

Khattab

Ali

El‐Sayed

2007

Heteroatom Chemistry

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Understanding the Influence of the Trifluoromethyl Group on the Selectivities of the [3+2] Cycloadditions of ThiocarbonylS‐methanides with α,β‐Unsaturated Ketones. A MEDT study

et al. 2020

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Experimentally (G. Mlostoń et al., J. Fluor. Chem. 2016, 190, 56–60), it has been found that the type of the obtained cycloadduct of the [3+2] cycloaddition (32CA) reaction of thiocarbonyl S‐methanides with α,β‐unsaturated ketones depends strongly on the location of the trifluoromethyl group. In the case of enones containing the CF3CH=CH moiety, the 32CA reaction occurs chemo‐ and regioselectively onto the C=C double bond giving trifluoromethylated tetrahydrothiophene derivatives. On the other hand, enones containing the CF3−C=O fragment react as carbonyl heteroethylenes leading to trifluoromethylated 1,3‐oxathiolanes also in a chemo‐ and regioselective manner. Our aim in the present work is to perform a theoretical study of the all chemo‐, regio‐, and stereo‐isomeric reaction paths of these 32CA reactions within the Molecular Electron Density Theory. Activation Gibbs free energies, calculated at the B3LYP/6‐311G(d,p) level in tetrahydrofurane at −40 °C, show that the ortho/endo reaction path giving the trifluoromethylated tetrahydrothiophene is more favoured, while the meta/endo reaction path leading to trifluoromethylated 1,3‐oxathiolanes is more preferred in total agreement with experimental findings. The low activation barriers in combination of the Electron Localization Function topological analysis of the most relevant points along the Intrinsic Reaction Coordinate reveals the pseudomonoradical character of the studied 32CA reactions.

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A Comparative Study of the Effect of Water and Organic Solvents on 1,3-Dipolar Cycloaddition Reactions of Mesitonitrile Oxide withC-Sulfonyl- and Sulfanyl-Dithioformates

El‐Sayed

Ali

Hawata

et al. 2010

Phosphorus, Sulfur, and Silicon and the Related Elements

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Generation and [2+3] Cycloadditions of a Sulfonylated Thiocarbonyl S-Methanide

Cited by 5 publications

References 19 publications

Generation and cyclization of thiocarbonyl S‐ylides by reaction of diazocompounds with C‐sulfonyldithioformates

Generation and cyclization of thiocarbonyl S‐ylides by reaction of diazocompounds with C‐sulfonyldithioformates

Understanding the Influence of the Trifluoromethyl Group on the Selectivities of the [3+2] Cycloadditions of ThiocarbonylS‐methanides with α,β‐Unsaturated Ketones. A MEDT study

A Comparative Study of the Effect of Water and Organic Solvents on 1,3-Dipolar Cycloaddition Reactions of Mesitonitrile Oxide withC-Sulfonyl- and Sulfanyl-Dithioformates

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