Thietane 1,1-dioxide ring

Thietane 1,1-dioxide ring from sulfonic acid chlorides O... 

The steric effect generated by the gem-dimethyl group of the thietane ring on the adjacent sp2 carbon atom makes the cycloaddition in these cases more sluggish compared with those of the parent thietane dioxide (6b)190. These cycloadditions provide a convenient entry into the strained thiabicyclo [2.2.0] hexane system (e.g. 287, 288 equation 107). 

It is difficult to decide whether the discrepancy between the calculated and experimental data is due to a different conformational preference of the thietane dioxides in the liquid and the solid phase, or to the crude approximations included in the Karplus-Barfield equation. However, the relationship between vicinal coupling constants and dihedral angles appears qualitatively valid in thietane oxides and dioxides, particularly if trends instead of exact values are discussed . At any rate thietane dioxides, 1,3-dithietane dioxides and tetroxides maintain either planarity or a slightly distorted average vibrating conformation with a low barrier to ring planarity . 

The proton spectra of thietane oxide (5a) and thietane dioxide (5b) have been studied in order to evaluate whether the oxidation at the sulfur atom changes the established 35° puckering of the ring , and whether a correlation is possible between structure and NMR parameters . 

Following a detailed NMR study of the 3-substituted thietane dioxides 188 it was concluded that the three-bond coupling constants can be safely used for stereochemical assignments in this series in particular the 7rih4<4Hz (Table 7, R =H, X = C) is consistent with an equatorial-equatorial interaction. This indicates an axial preference for the 3-substituent R (i.e. 188b) in both liquid and solid phases, and also suggests that the ring is puckered . 

Ethylmagnesium bromide tert-hutanol 1,2-Oxathiolane 2-oxides from thietane dioxides Stereospecific ring expansion... 

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