Domino‐Hydroformylation/Aldol Condensation Catalysis: Highly Selective Synthesis of α,β‐Unsaturated Aldehydes from Olefins

Abstract

A general and highly chemo-, regio-, and stereoselective synthesis of α,β-unsaturated aldehydes by a domino hydroformylation/aldol condensation reaction has been developed. A variety of olefins and aromatic aldehydes were efficiently converted into various substituted α,β-unsaturated aldehydes in good to excellent yields in the presence of a rhodium phosphine/acid-base catalyst system. In view of the easy availability of the substrates, the high atom-efficiency, the excellent selectivity, and the mild conditions, this method is expected to complement current methodologies for the preparation of α,β-unsaturated aldehydes.

An Unprecedented 5‐Connected Self‐penetrated Cadmium(II) Coordination Polymer: Synthesis, Crystal Structure, and Luminescent Property

“…Therefore, the combination of transition metal‐catalysed hydroformylation with further reactions is still a field of high interest in chemistry as seen in reports that have been recently published 3. The specific combination of hydroformylation with organocatalytic reactions is displayed only in few examples4 with a main focus on tandem hydroformylation/aldol reaction4a–d.…”

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

“…43 Additionally, in the work by Fang et al NaOH turned out to be an ineffective aldol catalyst, when used under hydroformylation conditions. 19 In the same work, the authors found a combination of pyrrolidine and benzoic acid to be the most successful aldol catalyst for their reaction system. The pyrrolidine enables enamine catalysis, while the benzoic acid accelerates the enamine formation.…”

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“…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.…”