Hydrogenation of Sulfoxides to Sulfides under Mild Conditions Using Ruthenium Nanoparticle Catalysts

Abstract

The first demonstration of the hydrogenation of sulfoxides under atmospheric H2 pressure is reported. The highly efficient reaction is facilitated by a heterogeneous Ru nanoparticle catalyst. The mild reaction conditions enable the selective hydrogenation of a wide range of functionalized sulfoxides to the corresponding sulfides. The high redox ability of RuO(x) nanoparticles plays a key role in the hydrogenation.

Selective liquid phase hydrogenation of furfural to furfuryl alcohol by Ru/Zr-MOFs

“…The role of RuO x in hydrogenation has also been discussed, for instance in lactose hydrogenation [66]. Mitsudome et al, suggested that the redox properties of surface Ru atoms in RuO x play a crucial role in hydrogenation of sulfoxides to sulfides under mild conditions [67]. Alternatively, we propose that such RuO x species may have already been reduced to metallic Ru upon exposure to H 2 under mild conditions.…”

“…Several factors have been proposed to explain the hydrogenation activity of supported Ru nanoparticles [59][60][61][62][63][64][65][66][67]: the Ru particle size, the interaction of the Ru nanoparticles with the support, and the redox properties of RuO x species. It has also been proposed that a minimum size of Ru particles is necessary for the adsorption of the substrate [29].…”

B(C6F5)3‐Catalyzed Deoxygenation of Sulfoxides and Amine N‐Oxides with Hydrosilanes

“…[5] The past decade has witnessed spectacular advances in metal-free catalytic reductions, particularly with the use of B(C 6 F 5 ) 3 /silanes. Over the past years, many systems have been employed for the deoxygenation of sulfoxides, including reagents such as silane/MoO 2 Cl 2 , [6] oxo complexes, [7] gold nanoparticles, [8] zinc(II) trifluoromethanesulfonate/bis(pinacolato)diboron [Zn(OTf ) 2 /B 2 (pin) 2 ] or Zn(OTf ) 2 /boranes, [9] SOCl 2 , [10] Fe powder, [11] ruthenium nanoparticles, [12] and I 2 . Over the past years, many systems have been employed for the deoxygenation of sulfoxides, including reagents such as silane/MoO 2 Cl 2 , [6] oxo complexes, [7] gold nanoparticles, [8] zinc(II) trifluoromethanesulfonate/bis(pinacolato)diboron [Zn(OTf ) 2 /B 2 (pin) 2 ] or Zn(OTf ) 2 /boranes, [9] SOCl 2 , [10] Fe powder, [11] ruthenium nanoparticles, [12] and I 2 .…”

“…Consequently, the combined use of B(C 6 F 5 ) 3 and hydrosilanes allows the deoxygenation of alcohols [3] and ethers [4] as well as carbonyl compounds and their derivatives. Over the past years, many systems have been employed for the deoxygenation of sulfoxides, including reagents such as silane/MoO 2 Cl 2 , [6] oxo complexes, [7] gold nanoparticles, [8] zinc(II) trifluoromethanesulfonate/bis(pinacolato)diboron [Zn(OTf ) 2 /B 2 (pin) 2 ] or Zn(OTf ) 2 /boranes, [9] SOCl 2 , [10] Fe powder, [11] ruthenium nanoparticles, [12] and I 2 . [2] In addition, the reduction of sulfoxides and amine N-oxides into their corresponding sulfides and amines is an important reaction owing to its considerable utility in organic synthesis.…”

“…[2] In addition, the reduction of sulfoxides and amine N-oxides into their corresponding sulfides and amines is an important reaction owing to its considerable utility in organic synthesis. [20] However, many of the reagents employed for these deoxygenation processes are expensive, [6,8,12] sensitive to both air and moisture, [15,17] or involve the use of transition metals under harsh conditions. [13] On the other hand, reagents used in the deoxygenation of amine Noxides include In, [14] Mo(CO) 6 , [15] Cu, [16] NbCl 5 /Zn, [17] Raney nickel, [18] diboron reagents, [19] and gold nanoparticles.…”