Heterogeneous and homogeneous catalysis for the hydrogenation of carboxylic acid derivatives: history, advances and future directions

Abstract

The catalytic reduction of carboxylic acid derivatives has witnessed a rapid development in recent years. These reactions, involving molecular hydrogen as the reducing agent, can be promoted by heterogeneous and homogeneous catalysts. The milestone achievements and recent results by both approaches are discussed in this Review. In particular, we focus on the mechanistic aspects of the catalytic hydrogenation and highlight the bifunctional nature of the mechanism that is preferred for supported metal catalysts as well as homogeneous transition metal complexes.

A General, Practical Triethylborane‐Catalyzed Reduction of Carbonyl Functions to Alcohols

“…As expected, in the presence of BEt 3 (5 mol %), no reactiont ook place between 1a and PMHS (3 equiv of SiÀHr elative to 1a)inE t 2 Oatroom temperature (Table 1, entry 1). However,w ith the additiono fN aOMe (5 mol %) the reactiono ccurred, and 2-phenylethanol( 2a)w as obtained in 99 %y ield (94 %i solatedy ield) after hydrolysis with NaOH (aq) and MeOH ( 4 ,w hichi sr esponsible for ester reductions. [14] However,u nder our condition (at ambient temperature),t he reaction of 1a with PMHS andK O tBu (5 mol %) in the absence of BEt 3 gave no reduction product 2a after 10 h( Ta ble 1, entry 9).…”

“…[1] Stoichiometric reactions using organometallic hydrides,s uch as LiAlH 4 ,N aBH 4 ,a nd DIBAL-H (diisobutylaluminium hydride), are prevalent on al aboratoryscale.…”

Selective Hydrogenation of Dodecanoic Acid to Dodecane-1-ol Catalyzed by Supported Bimetallic Ni-Sn Alloy

“…Interactions between metals in bimetallic catalysts can modify their surfaces, which can be beneficial for the conversion and upgrading of highly complex biomass derived compounds [7][8][9]. In previously published studies, several bimetallic alloy transition metal catalysts (e.g.…”

Hydrogenation of Levulinic Acid over Nickel Catalysts Supported on Aluminum Oxide to Prepare γ-Valerolactone

“…It is a typical procedure for hydrogenation of carboxylic acids, whereby some heterogeneous catalysts are successfully applied for the hydrogenation of a carboxylic acid to the corresponding product [10]. The first step in producing GVL is hydrogenation of LA to form an intermediate, followed by an intramolecular cyclization reaction.…”