Decreasing Side Products and Increasing Selectivity in the Tandem Hydroformylation/Acyloin Reaction

Abstract

A highly selective catalyst system was developed for the recently discovered tandem hydroformylation/acyloin reaction by systematic investigations and changes of reaction conditions. This new catalyst system is characterized by an excellent selectivity of the desired reaction pathway with negligible amounts of side products. A successful application of the tandem hydroformylation/acyloin reaction to a variety of olefins is enabled with comparable excellent selectivities up to >99 % for the first and second reaction step, therefore a general synthesis for the conversion of olefins into acyloins is found. Furthermore, very good to excellent yields for the intermediates and final acyloin products were observed within two catalysed reactions in one preparative step. The acyloin product was applied as a nonpolar precursor for surfactants. After attaching a polar head group to the acyloin and determination of tensiometric data, the molecule showed industrial relevant surface‐active properties.

Catalyst recycling in the hydroaminomethylation of methyl oleate: A route to novel polyamide monomers

“…Tandem catalyses are a hot topic in catalytic carbonylation reactions when it comes to increasing the efficiency of chemical processes, because it makes merging different reaction steps into a single preparative step possible, reducing waste while saving time and energy . Transition metal catalyzed tandem catalyses often involve hydroformylation as the initial reaction step to form reactive aldehydes , which constitutes a well investigated reaction that is also the subject ongoing research .…”

Recycling of two molecular catalysts in the hydroformylation/aldol condensation tandem reaction using one multiphase system

“…12,13 However, more common are tandem reactions in which hydroformylation is the first reaction step, followed by, hydrogenation (hydrohydroxymethylation), reductive amination (hydroaminomethylation), acetalization, acyloin reaction or aldol condensation (Scheme 1). 10,11,[14][15][16][17] The hydroformylation/aldol condensation tandem reaction allows the formation of α,β-unsaturated aldehydes, which are an important molecule class for cosmetics, agrochemicals and pharmaceuticals. 18 Nevertheless, it has received less attention compared to hydrohydroxymethylation or hydroaminomethylation.…”

Synthesis of Industrial Primary Diamines via Intermediate Diols – Combining Hydroformylation, Hydrogenation and Amination

“…The compatibility of the different reaction parameters required for each individual reaction step poses a significant challenge when it comes to developing new tandem catalysis reactions. Tandem reactions such as hydroaminomethylation, hydrohydroxymethylation,, aldol condensation or epoxidation all include a hydroformylation step to obtain the intermediate aldehyde, which then undergoes further conversions to achieve the desired product. Recent investigations using a rhodium and ruthenium catalyst have combined dcpd hydroaminomethylation with the dealkylation of the resulting secondary amines with ammonia to obtain TCD‐diamine.…”