Effective Precursors for Sulfur Monoxide Formation

Abstract

When triphenylmethanesulfenyl chloride (12) (or its thio 13 or dithio homolog 14) are treated with hindered olefins 15 and 16, thiiranes 10 and 11 are produced in high isolated yields (ca. 94%). Treatment of 10 and 11 with m-chloroperoxybenzoic acid (m-CPBA) leads to the formation of thiirane 1-oxides 8 and 9 (99% isolated yields). The structures of 8-11 were established by (1)H and (13)C NMR, mass spectrometry as well as by X-ray. Thermal decomposition of either 8 or 9 smoothly delivers sulfur monoxide to various 1,3-dienes giving cyclic sulfoxides in good yield. A variety of conditions were employed to optimize the yield of the trapped adducts.

Reactions of 9,9′‐bibenzonorbornenylidene sulfoxides with TMSOTf: Anomalous pinacol‐type rearrangement of thiirane 1‐Oxides

“…On the other hand, 2,2 -biadamantylidene sulfoxide 8d reacted with TMSOTf in refluxing toluene for 36 h to form 2,2 -biadamantylidene 5d and the recovery of 8d (entry 6). This reaction proceeded more SCHEME 2 slowly than that without TMSOTf, giving 5d as a sole product, reported by Harpp (entry 7) [6], indicating that TMSOTf seemed to prevent the extrusion of sulfur monoxide from 8. Using other reagents, such as BF 3 ·OEt 2 , Cu(OTf) 2 , and PdCl 2 , in place of TMSOTf in the reactions of 8a and 8b did not produce a satisfactory rearrangement.…”

“…The products of their thermal decomposition in solution seemed to vary with the kind of atom connecting with the sulfur atom in their thiirane ring. In general, heating a solution of thiirane 1-oxide results in the formation of the corresponding alkene with the extrusion of sulfur monoxide [4], which can be trapped with diene [5][6][7]. The C S bond dissociation of the thiirane 1-oxides seemed to proceed homolytically in the initial stage of thermal decomposition.…”

Reactivity of Small Oxoacids of Sulfur

“…For synthetic purposes in organic chemistry, sulfur monoxide can be received in situ, for example, from thiirane oxide [82] or a trisulfide-2-oxide [83]. SO can be trapped by dienes or metal complexes [84,85,86,87]. Thus, heating trisulfide oxide (1) in the presence of dienes (2) results in transfer of sulfur monoxide to form cyclic unsaturated sulfoxides (3) in good to excellent yields, along with recovery of disulfide (4) (Scheme 4) [83].…”

New Sulfenyl Chloride Chemistry: Synthesis, Reactions and Mechanisms toward Carbon-Carbon Double Bonds

“…In addition, we investigated [84,[86][87][88] the reaction of triphenylmethanesulfenyl chloride (2) and its thio 3 and dithio 4 homologs with more hindered olefins such as adamantylideneadamantane (48) In another study [84], we examined the reaction of triphenylmethanesulfenyl chloride (2) and its thio 3 and dithio 4 homologs with another series of olefins. Cyclic olefins such as 1,2-diphenylcyclohexene (63), 1,2-diphenylcyclobutene (64), 1,4-dimethylcyclohexene (65), (1R)-(þ)--pinene (66), (1S)-(À)--pinene (67), 3-carene (68), camphene (69), 3,4-dihydro-2H-pyran (70), 2,5-dihydrofuran (71) and 2,5-dimethoxy-2,5-dihydrofuran (72) did not react with the series of sulfenyl chlorides.…”