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3-Hydroxythietane derivatives undergo retro-aldol ring fission in aqueous sodium hydroxide at a rate determined by the substituent (H or Ph) at the 3 position and by the oxidation state of sulfur. Reactions occur between 4 × 104 and 5 × 105 times faster than for the open chain analogues. These rate accelerations correlate with an expression of strain energy between 41% and 33% compared with approximately 26% for alkene-forming eliminations of cyclobutanes. These differences, together with the differences in relative sensitivities to alpha-phenyl substitution and uniformly positive values of entropies of activation for 3-hydroxythietane derivatives, suggest a greater degree of ring cleavage in the transition structure for thietanes than for cyclobutanes. Ring fission is, however, accompanied by concomitant protonation of the leaving carbon group as evidenced by the isotope discrimination value of 1.7 for reaction of 3e. 3-Hydroxythietane itself does not undergo retro-aldol ring cleavage but rather anionic polymerisation to yield polymer 9a.

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Pathways in nucleophilic fission of hydroxythietanes are determined by the oxidation state of sulphur; for eliminative fission, activation parameters, substituent effects, and comparison with unstrained analogues all suggest a greater degree of ring cleavage in the transition structure for thietanes than for cyclobutanes.

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Carbon-13 chemical shifts of the alpha- and beta-carbon atoms for 12 thietane 1,1-dioxides, 9 thietane 1-oxides and 7 thietanes with a variety of 3-substituents are correlated according to the nature of the sulfur atom (Y=sulfone, sulfoxide, sulfide) and the nature of the 3-substituent (X) by the equations deltaalpha=aY+bX and deltabeta=aX+bY, where a and b are parameters characteristic of X and Y.One-bond coupling constants are reported for 21 compounds.The chemical shifts for the alpha- and the beta-carbon atoms of the sulfones show the “four-membered ring sulfone effect” (alpha-carbon unusually deshielded, beta-carbon unusually shielded), but the alpha-carbon-hydrogen coupling constants are similar to those of the sulfoxides and sulfides; the beta-carbon-hydrogen coupling constants are sensitive to the nature of the substituent (X) but no special beta-effect is observed.Comparison of the chemical shifts of the alpha-methylene carbon atoms of 3-phenyl-, 3-(beta-naphthyl)- and 3-(alpha-thienyl)-thietes with those of the corresponding sulfones also reveals the “four-membered ring sulfone effect” cis- and trans-3-substituted thietane 1-oxides may be distinguished by the greater downfield shift for the beta-carbon atom in the trans-isomer.

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Carbon-13 and Oxygen-17 Nuclear Magnetic Resonance Studies of Organosulfur Compounds: The Four-Membered-Ring Sulfone Effect

As revealed by carbon-13 and oxygen-17 NMR spectroscopy, thietane 1,1-dioxides and related four-membered-ring sulfonyl compounds show unusual alpha-carbon and sulfonyl oxygen deshielding and beta-carbon shielding when compared to other thiacycloalkane 1,1-dioxides and acyclic counterparts.

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Pathways in fission of strained rings

3-ring vs 4-ring reactivity ratios in the concerted cleavage of oxacycles are substantially smaller than for stepwise processes studied earlier but ratios are nevertheless much larger than strain energy differences could predict.In cleavage of hydroxycyclobutanes and of hydroxythietandioxides, activation parameters and substituent effects suggest a substantially greater degree of ring cleavage in the transition structure for the latter.For eliminative cleavage of a number of 3-substituted thietandioxides, there is no relationship between reactivity and the basicity of the 3-substituent; for “internal” carbon nucleophiles, however reactivities are in the order of the stabilising effects of substituents upon carbon-carbon double bonds.

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