Synthesis and configurational assignment of episulphoxides

Oxidative Addition von H2 und HCl an Iridium-Schwefelmonoxid- und Schwefeldioxid-Komplexe/ Oxidative Addition von H2 und HCl an Iridium-Schwefelmonoxid- und Schwefeldioxid-Komplexe

“…[(C sH 14) 2 R h C l] 2 [21], [(C 8 H 14) 2 IrC l] 2 [22], C2H 4SO [23] sowie die SO-K om plexe la , b [4] und die SO : -D erivate 2a, b [8 ] w urd en nach L iteratu ran g ab en hergestellt. …”

On the conformational preferences of the dehydrochlorination of α-chlorosulfoxides

“…Using the same assumptions as earlier, Scheme 5 depicts the only conformation available for the y-dehydrochlorination of each of 1hA and 1hB. Due to a rapid sigmatropic rearrangement, thiirane-S-oxide 17 is unattainable (10). However, anti-4-phenyl-l,2-epithiobutane-S-oxide (18) could be synthesized by a pathway similar to that portrayed in Scheme 4.…”

“…Thiirane-S-oxide 6 should be readily available from thiirane 15 by oxidation. Thiirane-S-oxide 9 would probably be inaccessible via oxidation of 15 since oxidation of cis-stilbenesulfide affords only the isomer where the sulfinyl oxygen is anti to the phenyl groups (10). The requisite thiiranes were prepared from 1-phenylpentyne (10) as indicated in Scheme 4.…”

“…The requisite thiiranes were prepared from 1-phenylpentyne (10) as indicated in Scheme 4. Not surprisingly, oxidation of 15 afforded only one product; it was assigned the structure of thiirane-S-oxide 6 (10). Compound 6 is a thermally sensitive species and all handling of it was done at temperatures lower than 0°C.…”

“…The major isomer was judged to be compound 8 based on the relative 'H NMR chemical shifts of the ring hydrogens of 7 and 8 (10). Separation of these isomers was impossible owing to their instability.…”