Sulfonimidoyl group

Fig. 1.3.1 Fine-tuning of the properties of the sulfonimidoyl group through choice of the N-substituent(s).

The structure of the sulfonimidoyl-substituted homoallyl alcohols 4-7 in solution and in the crystal is characterized by an intramoleculare hydrogen bond between the OH group and the N atom of the sulfonimidoyl group. 

According to NMR spectroscopy, complexes -16 have a low configurational stability of the Ca atoms, giving rise to the formation of a mixture of the diaste-reomeric complexes Rs,Sc-16 and Rs, cT6 (Schemes 1.3.13 and 1.3.14). Addition of the Lewis acids Ti(OiPr)4 and ClTi(OiPr)3 causes their coordination to one of the sulfonimidoyl groups and establishment of an equilibrium between the cor-... 

The sulfonimidoyl group acts in the asymmetric synthesis of the unsaturated oxiranes shown in Schemes 1.3.20 and 1.3.21 as both a chiral auxiliary and a nucleofuge. These results suggested the application of the sulfonimidoyl group as a chiral linker in solid-phase synthesis. 

Stabilized lithiated sulfoximines (112) undergo highly diastereoselective Michael additions to cyclic enones at —78 °C under kmetically controlled conditions. At room temperature, the initially formed adducts (113) undergo intramolecular substitution of the sulfonimidoyl group, with inversion of configuration to afford the corresponding cyclopropanes (114).92... 

Treatment of 77 with LDA at -78 °C followed by warming the reaction mixture to room temperature for 1 h gave the diastereomerically pure cyclopropane 75a in 60% yield. Surprisingly, oxirane products, which could potentially arise from nucleophilic displacement of the sulfonimidoyl group by the alkoxide in 78 (see... 

Boidwell estimated the pKa of A 3-dimethyl-5-phenylsulfoximine (141) in DMSO to be about 33, less acidic than methyl phenyl sulfone by about 4 pK units. From a cyclopropyl effect on the equilibrium acidity of Af-phenylsulfonyl-5-methyl-5-phenylsulfoximine (142), it was concluded that the carbanion is planar or nearly planar to the sulfonimidoyl group.However, on the basis of the 7ch coupling constant in a NMR spectroscopic study, it was concluded by Marquet that the configuration of the lithi-ated a-carbon (142) is pyramidal. ... 

---