Selective Production of Linear Aldehydes and Alcohols from Alkenes using Formic Acid as Syngas Surrogate

Abstract

Performing carbonylation without the use of carbon monoxide for high‐value‐added products is an attractive yet challenging topic in sustainable chemistry. Herein, effective methods for producing linear aldehydes or alcohols selectively with formic acid as both carbon monoxide and hydrogen source have been described. Linear‐selective hydroformylation of alkenes proceeds smoothly with up to 88 % yield and >30 regioselectivity in the presence of single Rh catalyst. Strikingly, introducing Ru into the system, the dual Rh/Ru catalysts accomplish efficient and regioselective hydroxymethylation in one pot. The present processes utilizing formic acid as syngas surrogate operate simply under mild condition, which opens a sustainable way for production of linear aldehydes and alcohols without the need for gas cylinders and autoclaves. As formic acid can be readily produced via CO2 hydrogenation, the protocols represent indirect approaches for chemical valorization of CO2.

Iron‐Catalyzed Magnesium‐Mediated Formal Hydroformylation of Alkynes and Alkenes

“…As DMF is easily accessible, we decided to use DMF for our further screening. Subsequently, the effect of an in-situ added ligand (L1-L10) on the conversion/yield of the reaction was investigated (Table 1, entries [15][16][17][18][19][20][21][22][23][24]. Although a slight increase in yield was observed in the presence of ligand, the improvement was only marginal and insignificant.…”

“…[41] Next, iron precursors such as, [Fe(OAc) 2 ], [Fe(OTf) 2 ], [FeCl 2 ], [FeBr 2 ], [FeCl 3 ], with L5 were examined. Among various iron precursors, [Fe(acac) 3 ] displayed the highest conversion and yield (Table 3, entry 7 vs entries [13][14][15][16][17]. Use of ethyl magnesium chloride or propyl zinc bromide did offer any improvement (Table 3, entries [18][19].…”

“…[13] Although the process is being industrially practiced, it faces safety challenges, is associated with higher operational costs, and poses severe limitations. [14,15] The LPO is not widely accessible as it requires additional infrastructure and is confined to a privileged few laboratories. [16] As a result, significant emphasis has been given to the development of reactions with CO surrogates.…”

“…With one to two exceptions, high syngas pressure and high temperatures are needed for iron‐catalyzed hydroformylation [13] . Although the process is being industrially practiced, it faces safety challenges, is associated with higher operational costs, and poses severe limitations [14,15] . The LPO is not widely accessible as it requires additional infrastructure and is confined to a privileged few laboratories [16] .…”

Regioselective Hydroxymethylation of Alkenes to Linear Alcohols with CO2/H2 Using a Rh/Ru Dual Catalyst

“…In addition, hydroxymethylation using CO 2 /H 2 is a multiple-step process with distinct requirements of catalysts for each step, and it is always difficult to efficiently implement all the steps with one single-metal catalyst. Therefore, heterobimetallic catalysts would be preferred, as each of which could operate one reaction with high efficiency. − …”