Synthesis and structural characterization of chiral thiacrowns: the crystal and molecular structure of (R,R,R)-2,6,10-trimethyl-1,5,9-trithiacyclododecane

The chiral polythioether macrocycles (R,R,R)-2,6,10-trimethyl-1,5,9-trithiacyclododecane [(R,R,R)-Me312S3] (8), and (R,R,R,R)-2,6,10,14-tetramethyl-1,5,9,13-tetrathiacyclohexadecane, [(R,R,R,R)-Me416S4] (9), have been synthesized from (R)-2-methylthietane (7) by using the dirhenium carbonyl catalyst Re2(CO)9[(R)-2-SC(H)MeCH2CH2)] (10). The catalytic activity is low, 0.21 turnovers per hour, but is significantly above the uncatalyzed level. Compound 8 was characterized by a single-crystal X-ray diffraction analysis that was able to establish the absolute configuration.