Cover Picture: High‐Yielding Tandem Hydroformylation/Hydrogenation of a Terminal Olefin to Produce a Linear Alcohol Using a Rh/Ru Dual Catalyst System (Angew. Chem. Int. Ed. 26/2010)

Abstract

A volleyball is hit from the academic to the industrial side of the net and symbolizes the potential utility of a new dual catalyst system—a combination of xantphos/[Rh(acac)(CO)2] and Shvo's catalyst—in both fields. In their Communication on page ff. K. Nozaki et al. describe the highly efficient production of n‐undecanol using syngas and this catalytic system. The one‐pot process involves hydroformylation catalyzed by rhodium and hydrogenation catalyzed by ruthenium.

Hydrogenation of butanal over silica-supported Shvo’s catalyst and its use for the gas-phase conversion of propene to butanol via tandem hydroformylation and hydrogenation

“…T = 363 K, P Total = 1 atm, catalyst mass = 0.3 g, total gas flow rate = 100 cm 3 min À1 . (species E of Scheme 1) results from the reaction of species B with SX [17]. However, the possibility that both phosphorus atoms of SX are coordinated to Ru cannot be ruled out on the basis of the present data.…”

“…3 shows the results of solid-state 31 P MAS NMR measurements of spent SX-Shvo/SiO 2 which exhibits the same spectral features of the fresh SX-Shvo/SiO 2 . The broad peak observed at À13 ppm can be ascribed to the free SX adsorbed on the silica surface [13], while the broad peak centered at 34 ppm is due to the phosphine bonded to Ru as shown in species E [17]. Although many of species shown in Scheme 1 could undergo ligand exchange with SX, Reaction 5 is the most facile because of the vacant coordination site on species B.…”

“…It was noted, though, that the hydrogenation of the aldehyde would only occur after the CO was consumed or removed from the reactor because the Ru complex was inhibited by CO [16]. More recently, Nozaki and coworkers have demonstrated that it is possible to carry out the hydroformylation of propene to butanal and the subsequent hydrogenation of butanal to butanol in a solution containing a Rh complex, Shvo's catalyst, and bidentate phosphine ligand, sulfoxantphos (SX) [17]. Using this approach, butanol yields of up to 85% were obtained [17].…”

“…More recently, Nozaki and coworkers have demonstrated that it is possible to carry out the hydroformylation of propene to butanal and the subsequent hydrogenation of butanal to butanol in a solution containing a Rh complex, Shvo's catalyst, and bidentate phosphine ligand, sulfoxantphos (SX) [17]. Using this approach, butanol yields of up to 85% were obtained [17]. The authors suggest that the presence of excess SX influences the activity and/or the chemoselectivity of Shvo's catalyst to preferentially hydrogenate aldehydes [17].…”

“…Using this approach, butanol yields of up to 85% were obtained [17]. The authors suggest that the presence of excess SX influences the activity and/or the chemoselectivity of Shvo's catalyst to preferentially hydrogenate aldehydes [17]. These findings motivated us to explore the possibility of supporting Shvo's catalyst on silica in order to produce a heterogeneous catalyst that could be used in a tandem, gas-phase hydroformylation-hydrogenation process.…”