Production of alcohols via hydroformylation

Abstract

The numerous approaches for the catalytic synthesis of alkyl alcohols using an intermediate hydroformylation step are reviewed.

Acid‐Promoted Hydroformylative Synthesis of Alcohol with Carbon Dioxide by Heterobimetallic Ruthenium‐Cobalt Catalytic System

“…To examine our tentative idea, the turnover numbers (TONs) of RWGS by [Ru(CO) 3 Cl 3 ] À from in-situ [Ru(CO) 3 Cl 2 ] 2 splitting with [Bmim]Cl in the presence of different acids were measured (Table 1). Compared with the result in acid-free conditions (entry 1), adding acetic acid, benzoic acid, formic acid, phosphoric acid or para-toluenesulfonic acid could significantly elevate the RWGS efficiency of [Ru(CO) 3 Cl 3 ] À catalyst at low temperature (entries 2-6). Contrarily, the addition of hydrogen chloride, sulfuric acid or trifluoroacetic acid inhibited CO formation (entries 7-9).…”

“…The distinct results among three carboxylic acid additives [18] indicated that moderate acidity was beneficial to promote RWGS and that strong acidity might impede the formation of reductive ruthenium hydride anion. [19] Additionally, the catalytic efficiency of [Ru(CO) 3 Cl 2 ] 2 in the absence of chloride additive was much lower than [Ru (CO) 3 Cl 3 ] À . The presence of Co 2 (CO) 8 had little impact on the performance of ruthenium catalyst (details see Table S4 in SI).…”

“…[10] However, the intricate transformations from neutral pre-catalyst to various anionic active species are hard to be regulated and confine the elevation of efficiency on RWGS. [11] In comparison, [Ru(CO) 3 Cl 3 ] À was an effective RWGS catalyst with well-defined structure evolution during the reaction. [12] Its capability in carbonyl reduction was largely unexplored.…”

“…Based on our research interest on reductive conversion of CO 2 , [13] we intended to exploit its application in the reductive hydroformylation with CO 2 . Inspired by the promoting effect of acidic support on heterogeneous RWGS [14] and the benefits of basic conditions on homogeneous WGS, [15] we conceived that adding appropriate acid would enhance the performance of [Ru (CO) 3 Cl 3 ] À in low-temperature RWGS, thus improve the overall efficiency of reductive hydroformylation with CO 2 .…”

Rhodium/Phosphine catalysed selective hydroformylation of biorenewable olefins

“…Since it was invented by Otto Roelen in 1938, this transformation has been widely explored and has made great progress in recent decades . It is also called as oxo process for the conversion of olefins into aldehydes, alcohols, carboxylic acid and derivatives in presence of transition metal catalyst under syngas (CO/H 2 ) pressure . It is atom economical process, however it has challenges in controlling the selectivity of products, isomerisation and hydrogenation .…”