Cyclopropyl thioethers

Similar studies on the gas phase chemistry of cyclopropyl thioethers were reported by Chizhov et The conclusions drawn in the investigation were, however, hampered by the fact that protonation seems to occur competitively at both the cyclopropane ring, the sulphur atom and the aryl ring. 

The same protocol shown in Scheme 123 was used with cyclopropyl phenyl thioether, so cyclopropylic 1,3-diols 444 were obtained in 31-53% yield °. ... 

Simple side-chain reactions of 1,2-dithiin diols have been conducted. Besides the formation of esters, ethers (R = Me, Et, 7-Pr, cyclopropyl, Ph, pyridyl, cyclopentyl), and thioethers (R = H, TBDMS R = 4 -(4-hydroxyphenyl)-l//-tetrazole-5-thiol), selective oxidation of the primary alcohol groups in the presence of the 1,2-dithiin heterocycle could be readily achieved (Scheme 36) <1995JME2628, 1994SL201>. Additionally, amides, ureas, and carbamates of the dithiin diol were synthesized <1995JME2628>. 

Sulfur ylides have been used to generate bicyclic macrolactams, as shown in Scheme 35. Argogel-bound thioacetic acid 130 was synthesized from thioacetic acid esters by alkylation with Argogel-Cl resin and subsequent basic hydrolysis of the ester (not shown in Scheme 35). Esterification with co-hydroxy vinyl ketone 131 gave intermediate 132. Alkylation with MeOTf activated the thioether and reaction of 133 with DBU in CH2CI2 at room temperature provided the macrocycle 134 containing an additional cyclopropyl unit in 52 % yield as the pure trans diastereoi-somer [51]. 

The behaviour with acids of the cyclopropyl sulphoxide (173X obtained with its diastereoisomer by peracid oxidation of the corresponding thioether, is unusual. With weak acids (acetic, benzoic, etc.) the ring-cleaved sulphoxide (174) is produced whereas with strong acids (or bases) geometrical isomerization occurs (Scheme 20). The... 

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