Journal of the American Chemical Society p. 4770 - 4778 (2002)
Update date:2022-08-04
Topics:
Sauve, Anthony A.
Groves, John T.
The compound [Ru(salen)(NO)(H2O)](SbF6) (1) (salen = N, N′-ethylene-bis-salicylidene aminate) reacts catalytically with thiiranes and converts them to olefins and 1,2,3,4-tetrathianes or 1,2,3-trithiolanes. The monosubstituted thiiranes styrene sulfide and propylene sulfide reacted to form the corresponding olefin and the 4-substituted 1,2,3-trithiolane in a 2:1 ratio in isolated yields in excess of 90%. The disubstituted thiirane cis-stilbene sulfide was converted to cis-stilbene and 5,6-trans-1,2,3,4-diphenyltetrathiane in a 3:1 ratio in the presence of a catalytic amount of 1 in CD3NO2. Coordination of cis-stilbene sulfide to the salen complex in a ligand substitution reaction was established by isolation of [Ru(salen)(NO)(cis-stilbene sulfide)]-(SbF6) (6). 1H NMR studies performed on 6 indicated that the salen macrocycle had rearranged upon thiirane coordination. A similar rearrangement was found to be stabilized by other ligands including tetramethylethylene sulfide, tetrahydrothiophene, and d3-acetonitrile. The α-deuterio-cis-stilbene sulfide catalyst adduct (d-6) reacted with unlabeled cis-stilbene sulfide to form deuterium-labeled trans-diphenyl-tetrathiane and unlabeled cis-stilbene as shown by GCMS and 1H NMR. Thus, the solution thiirane behaves as a sulfur donor and forms olefin, whereas the coordinated thiirane becomes the cyclic polysulfide. β-cis-Deuteriostyrene sulfide was used to show that ring closure to form cyclic polysulfide incorporated inversion of stereochemistry versus starting thiirane. A mechanism for catalysis consistent with experimental data is presented that requires coordination of thiirane to the metal complex followed by bimolecular attack of free thiirane on the coordinated thiirane.
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Doi:10.1021/jo01352a610
(1957)Doi:10.1021/acs.orglett.8b01591
(2018)Doi:10.1021/ja807613q
(2008)Doi:10.1021/jacs.6b01533
(2016)Doi:10.1002/ejoc.200800451
(2008)Doi:10.1021/ja01125a051
(1952)