- DISTINGUISHING IONIZATION FROM SULFUR P-TYPE LONE PAIR ORBITALS AND CARBON ?-MOLECULAR ORBITALS BY He I/He II PHOTOELECTRON SPECTROSCOPY
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He I and He II photoelectron spectra of methylthiomethylbenzene (2), 2-(1-methylethylthio)ethylbenzene (3), 1-naphthalenemethanethiol (4), 1,1-dimethylethylthiobenzene (5), benzenethiol (6), and methylthiobenzene (7) are reported.Comparison of the He I and He II band areas for each compound provide a reliable basis for assigning the bands as due to photoionization from a carbon ?-molecular orbital, sulfur p-type lone pair orbital, or mixed orbital.Ionization from a molecular orbital localized on sulfur results in a large decrease in intensity using He II compared with He I as the source relative to ionization from carbon ?-molecular orbitals.Mixed orbitals with both sulfur and carbon character also give rise to diminished intensities in the He II versus He I spectra relative to pure carbon orbitals, but proportionately less decrease than pure sulfur orbitals.
- Glass, Richard S.,Broeker, Jeffrey L.,Jatcko, Mark E.
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- Stable and easily available sulfide surrogates allow a stereoselective activation of alcohols
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Isothiouronium salts are easily accessible and stable compounds. Herein, we report their use as versatile deoxasulfenylating agents enabling a stereoselective, thiol-free protocol for synthesis of thioethers from alcohols. The method is simple, scalable and tolerates a broad range of functional groups otherwise incompatible with other methods. Late-stage modification of several pharmaceuticals provides access to multiple analogues of biologically relevant molecules. Performed experiments give insight into the reaction mechanism.
- Brutiu, Bogdan R.,Drescher, Martina,Matya?ovsky, Ján,Maulide, Nuno,Merad, Jérémy,Pinto, Alexandre,Stopka, Tobias
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p. 7770 - 7774
(2021/06/16)
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