Palladium-Catalyzed Coupling Reaction of Diaryl Dichalcogenide with Aryl Bromide Leading to the Synthesis of Unsymmetrical Aryl Chalcogenide

Abstract

An efficient cross-coupling reaction of diphenyl disulfide or diselenide with substituted aryl bromides using PdCl₂(dppf) and zinc has been developed. This method gave functionalized unsymmetrical aryl sulfides and selenides in good to excellent yields under neutral conditions.

sulfur - selenium - palladium - cross-coupling - catalysis

References and Notes

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<A NAME="RU06806ST-10">10</A>

The copper-catalyzed reaction of bromobenzene with diphenyl disulfide produced only a 34% yield of diphenyl sulfide. See ref. 7a.

<A NAME="RU06806ST-11">11</A>

Typical experimental procedure: Diphenyl disulfide (109 mg, 0.5 mmol), PdCl₂(dppf) (37 mg, 0.05 mmol), and zinc (80 mg, 1.2 mmol), were placed in a round-bottom flask containing a stirring bar, and a THF solution (5 mL) of the aryl bromide (1.0 mmol) was then added to the flask, and the resulting mixture was heated at reflux for 24 h. After cooling to r.t., the mixture was diluted with Et₂O (30 mL). The precipitate was removed by filtration and the filtrate was washed with brine and dried (Na₂SO₄). A GC-MS analysis of the ethereal solution showed the presence of the corresponding unsymmetrical sulfide, and the yield was determined using biphenyl as an internal standard. The aryl sulfide was isolated by PTLC and fully characterized.

<A NAME="RU06806ST-12">12</A>

The reaction with p-iodonitrobenzene proceeded to give the corresponding aryl sulfide in 82% yield.

<A NAME="RU06806ST-13">13</A>

Magnesium was used instead of zinc for the reaction with 2-bromothiophene.

<A NAME="RU06806ST-14">14</A> Adapa et al. reported the stoichiometric coupling reaction between aryl bromides with diphenyl diselenides using CsOH. See: Varala R. Ramu E. Adapa SR. Bull. Chem. Soc. Jpn.  2006,  79:  140 

The Se-Se bond in diphenyl diselenide was reductively cleaved by low valent indium and the generated selenoindium species react with alkyl halides (not aryl) to give alkyl aryl selenides. See:

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<A NAME="RU06806ST-16">16</A> The ruthenium-catalyzed coupling reaction of diphenyl diselenide with alkyl halides in the presence of zinc has been reported, where cleavage of the Se-Se bond takes place. See: Zhao X. Yu Z. Yan S. Wu S. Liu R. He W. Wang L. J. Org. Chem.  2005,  70:  7338