Disulfidation of Alkynes and Alkenes with Gallium Trichloride

Abstract

[reaction: see text] Treatment of diphenyl disulfide and terminal alkynes with gallium trichloride afforded (E)-1,2-diphenylthio-1-alkenes selectively (E/Z > 20/1). Alkenes also underwent this reaction to form trans adducts.

Unusual Influence of the Structures of Transition Metal Complexes on Catalytic C–S and C–Se Bond Formation Under Homogeneous and Heterogeneous Conditions

“…(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) so far been developed, including halogen substitution in vinyl halides, [5] preparation from olefins [6] and carbonyl [7] compounds, rearrangement of propargylic aryl chalcogenides, [8] selenodecarboxylation, [9] utilization of In, [10] Al, [11] Li, [12] Ti, [13] and Ga [14] reagents, and some other methods. [1] The best solution to the problem would be provided by addition reactions of element-hydrogen (E-H) and elementelement (E-E) bonds to easily available acetylenic hydrocarbons (E = S, Se).…”

Chalcogenoacetylenes Obtained by Indium(III) Catalysis: Dual Catalytic Activation of Diorgano Dichalcogenides and Csp–H Bonds

“…In this case, the formation of 1,2-diphenylseleno-1-alkenes was identified by GC-MS, which occurs in an analogous fashion to that of related diorgano disulfides employing GaCl 3 . [27,28] From these experimental results, we can conclude that In III works as a Lewis acid in the heterolytic cleavage of the Se-Se bond.…”

“…Initially, InCl 3 reacts with R 2 YYR 2 (Y = S, Se, and Te) to form R 2 YIn III Cl 2 (1) and R 2 YCl through heterolytic cleavage of the Y-Y bond. [27] The obtained R 2 YIn IIICl 2 then coordinates to the terminal alkyne via π complex 2. [26] Next, the activated hydrogen is removed by the base to form alkynyl chalcogen indium(III) intermediate 3, which produces the desired product and InCl according to path A through reductive elimination.…”

Recent applications of gallium and gallium halides as reagents in organic synthesis

“…87,88 Usigi et al found that treatment of diphenyl disulfide and terminal alkynes with gallium chloride affords (E)-1,2-diphenylthio-1-alkenes selectively (Scheme 40). 89 Alkenes can be transformed in a similar fashion, affording the trans adduct. The results 20 of the addition of diphenyl disulfide to various alkenes in the presence of Ga(III) chloride are summarised in Table 23.…”