High‐Yielding Tandem Hydroformylation/Hydrogenation of a Terminal Olefin to Produce a Linear Alcohol Using a Rh/Ru Dual Catalyst System

Abstract

A dual catalyst system has been developed for tandem hydroformylation/hydrogenation to produce n‐undecanol from 1‐decene in one pot. A combination of xantphos/[Rh(acac)(CO)2] and Shvo's catalyst (1) afforded the best results (see scheme; acac=acetylacetonate, DMA=N,N‐dimethylacetamide). Polar solvents effectively suppressed the formation of undecyl formate.

Auto-tandem catalytic reductive hydroformylation with continuous multiphase catalyst recycling

“…12,13 To achieve such a one-step synthesis, tandem catalysis is necessary. Several catalytic systems capable of so called “reductive hydroformylation” are known in the literature: orthogonal systems, using separate catalysts for either reaction step 14,15 and assisted systems, where each step is carried out under different reaction conditions with the same or a trigger-modified catalyst. 6…”

Ruthenium‐Catalyzed Hydroformylation of Alkenes by using Carbon Dioxide as the Carbon Monoxide Source in the Presence of Ionic Liquids

“…[17][18][19][20] However, the use of Rh-Ru bimetallic systems is of interest for the production of alcohols by hydroformylation/hydrogenation se-quences. [21][22][23][24][25] The differences in selectivity could be easily understood if we look at the hydroformylation and hydrogenation mechanisms catalyzed by Rh I and Ru 0 systems, as the active catalytic species under hydroformylation conditions are the RhÀH and the RuÀ(H) 2 species. [7][8][9]26] The accepted mechanism for the formation of MÀ(H) 2 is the homolytic cleavage of the HÀH bond, as the formation of MÀH occurs either by intramolecular (ligands) or intermolecular (external base) heterolysis of the HÀH bond, which favors the formation of MÀH species.…”

“…[29][30][31][32][33][34] The effect of the solvent is important because it was proposed that for Rh-catalyzed hydroaminomethylation reactions with the use of imidazolium ionic liquids (ILs) as the reaction media, the acidic protons of the imidazolium ring could shift the equilibrium between RhÀH and [RhÀ (H) 2 ] + to the formation of the hydrogenation catalytically active [RhÀ(H) 2 ] + species. [28] This hypothesis was confirmed by the observation that the presence of 3-alkyl-1,2-dimethylimidazolium salts slowed the hydrogenation rates.The potential use of Ru as a hydroformylation catalyst is of interest, as Rh is much less abundant, [7][8][9] and several Ru-catalyzed processes involving hydroformylation/hydrogenation [21][22][23][24][25] and hydroaminomethylation [17] were recently developed. However, a much more interesting system is that which can catalyze cascade reactions (i.e., CO 2 reduction to CO, hydroformylation, and hydrogenation sequence to produce alcohols of high added value).There are reports that this process is viable if either a Ru-based system with LiCl salts dissolved in N-methylpyrrolidone [35][36][37] or a biphasic imidazolium ILs/toluene [38][39][40][41] (Figure 1) system is used.…”

“…The potential use of Ru as a hydroformylation catalyst is of interest, as Rh is much less abundant, [7][8][9] and several Ru-catalyzed processes involving hydroformylation/hydrogenation [21][22][23][24][25] and hydroaminomethylation [17] were recently developed. However, a much more interesting system is that which can catalyze cascade reactions (i.e., CO 2 reduction to CO, hydroformylation, and hydrogenation sequence to produce alcohols of high added value).There are reports that this process is viable if either a Ru-based system with LiCl salts dissolved in N-methylpyrrolidone [35][36][37] or a biphasic imidazolium ILs/toluene [38][39][40][41] (Figure 1) system is used.…”

Domino Reactions Triggered by Hydroformylation

“…In these, only one metal is used as the catalyst for two different reactions although under drastic reaction conditions. The Rh/Ru dual catalyst 110 system has been developed to obtain high regioselectivity and yields using N,N-dimethylacetamide (DMA) as the solvent at 120 C for 12 h in the presence of 20 atm of syngas (Scheme 21) [49]. In this protocol, Rh(acac)(CO) 2 and XANTPHOS form the catalytically active specie for the HF, while Ru complex produces the reduction of the aldehyde.…”