Einfache und ergiebige Darstellungsmethoden für
            <i>N</i>
            ‐alkylierte Sulfoximide (Alkylimino‐oxo‐dialkyl‐sulfurane)

Schmidbaur, Hubert; Kammel, Gernot

doi:10.1002/cber.19711041029

Cited by 22 publications

(4 citation statements)

References 6 publications

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“…N , S , S ‐Trimethylsulfoximine (2d): 14 General Procedure 1 and Workup B were applied by using S , S ‐dimethylsulfoximine ( 1d ; 931 mg, 10 mmol). Silica gel column chromatography with methanol/ethyl acetate (5:95) as eluent afforded the title compound as a clear colorless oil (760 mg, 7.1 mmol, 71 %).…”

Section: Methodsmentioning

confidence: 99%

Iron‐Catalyzed Acylative Dealkylation of N‐Alkylsulfoximines

2015

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Section: Methodsmentioning

confidence: 99%

Iron‐Catalyzed Acylative Dealkylation of N‐Alkylsulfoximines

2015

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“…While the N -methyl derivative E - 3a has a 1 J (C,H) value of 155 Hz, the value for C-1 of the N -SO 2 CF 3 derivative 4 , which carries the stronger electron-withdrawing sulfonimidoyl group, is 169 Hz as a solution in [D 8 ]-toluene together with LiBF 4 , was studied by NMR spectroscopy . Ylide 10 showed for the methylene group a 1 J (C,H) value of 168 Hz (Table ), which is similar in magnitude to those recorded for ylides E - B .…”

Section: Resultsmentioning

confidence: 54%

Dynamic Behavior of Chiral Sulfonimidoyl-Substituted Allyl and Alkyl (Dimethylamino)titanium(IV) Complexes: Metallotropic Shift, Reversible β-Hydride Elimination/Reinsertion, and ab Initio Calculations of Allyl and Alkyl Aminosulfoxonium Ylides

et al. 2005

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Variable-temperature (1)H and (13)C NMR spectroscopy of the sulfonimidoyl-substituted allyltitanium(IV) complexes E-1a-c and Z-1a-c, which carry diethylamino groups at the Ti atom, revealed a fast 1,3-C,N-shift of the Ti atom, leading to an equilibrium between the epimeric Calpha-titanium allyl complexes A and C and the N-titanium allyl aminosulfoxonium ylide B. Based on these findings a model for the reactions of E-1a-c and Z-1a-c with aldehydes is proposed, which features regio- and diastereoselective reactions of the N-titanium ylide B at the alpha-position and the Calpha-titanium complex A at the gamma-position. Model ab initio calculations of the methylene and allyl (dimethylamino)sulfoxonium ylides 10 and 14, respectively, revealed short Calpha-S bonds, a stabilization by both electrostatic interaction and negative hyperconjugation, and a low Calpha-S rotational barrier. The ylides preferentially adopt Calpha-S and Calpha-N conformations in which the lone pair orbital at the Calpha atom is periplanar to the S=O bond and that at the N atom periplanar to the Calpha-Ph bond. Variable-temperature NMR spectroscopy of the sulfonimidoyl-substituted alkyltitanium(IV) complex 16, which carries diethylamino groups at the Ti atom, revealed a dynamic behavior leading to a complete topomerization of all four methylene hydrogens of the Calpha-ethyl groups. Two fast processes are held responsible for the topomerization of the hydrogens of 16. The first one is a reversible intramolecular beta-hydride elimination/alkene-Ti-H insertion with the intermediate formation of a complex between (Et(2)N)TiH and a 1-alkenyl sulfoximine, and the second one consists of a reversible 1,3-C,N-shift of the Ti atom in combination with a Calpha-S bond rotation. Interestingly, the room-temperature NMR spectra of the corresponding sulfonimidoyl-substituted alkyltitanium(IV) complex 17, which carries isopropoxy groups at the Ti atom, give no indication of a similar dynamic behavior of this complex.

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“…The IR spectrum unambiguously demonstrated the presence of a sulfonimidoyl moiety by displaying classificatory absorption bands at 1241 and 1149 cm −1 for the S=O and S=N vibration, respectively [11]. Absorption bands at 3258 and 2221 cm ORTEP projection of (R)-4 obtained by single-crystal X-ray diffraction with ellipsoids shown at 50% probability level (one associated molecule of acetonitrile omitted for clarity) [12].…”

Section: Open Accessmentioning

confidence: 99%