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Toward a mild dehydroformylation using base-metal catalysis † † Electronic supplementary information (ESI) available. See DOI: 10.1039/c6sc04607j Click here for additional data file.

View Article: PubMed Central - PubMed

ABSTRACT

Dehydroformylation, or the reaction of aldehydes to produce alkenes, hydrogen gas, and carbon monoxide, is a powerful transformation that is underdeveloped despite the high industrial importance of the reverse reaction, hydroformylation. Interestingly, nature routinely performs a related transformation, oxidative dehydroformylation, in the biosynthesis of cholesterol and related sterols under mild conditions using base-metal catalysts. In contrast, chemists have recently developed a non-oxidative dehydroformylation method; however, it requires high temperatures and a precious-metal catalyst. Careful study of both approaches has informed our efforts to design a base-metal catalyzed, mild dehydroformylation method that incorporates benefits from each while avoiding several of their respective disadvantages. Importantly, we show that cooperative base metal catalysis presents a powerful, mechanistically unique approach to reactions which are difficult to achieve using conventional catalyst design.

No MeSH data available.


Hydroformylation is a highly important industrial reaction.
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fig1: Hydroformylation is a highly important industrial reaction.

Mentions: Hydroformylation, the addition of a unit of H2 and CO across an olefin to form a branched or linear aldehyde (Fig. 1), is a reaction that has been known and well-studied since its serendipitous discovery in 1938 by Otto Roelen.1 This “oxo process” is an important method of synthesis with industrial output of >10 000 000 tons per year (Fig. 1).2 So called “oxo chemicals”, either aldehydes or alcohols and olefins derived from further hydrogenation and manipulation, are important products for a multitude of industrial applications and processes. Stemming from this importance, the reaction has remained the subject of significant scientific efforts with advances continuing to be made.1b,3


Toward a mild dehydroformylation using base-metal catalysis † † Electronic supplementary information (ESI) available. See DOI: 10.1039/c6sc04607j Click here for additional data file.
Hydroformylation is a highly important industrial reaction.
© Copyright Policy - open-access
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC5384452&req=5

fig1: Hydroformylation is a highly important industrial reaction.
Mentions: Hydroformylation, the addition of a unit of H2 and CO across an olefin to form a branched or linear aldehyde (Fig. 1), is a reaction that has been known and well-studied since its serendipitous discovery in 1938 by Otto Roelen.1 This “oxo process” is an important method of synthesis with industrial output of >10 000 000 tons per year (Fig. 1).2 So called “oxo chemicals”, either aldehydes or alcohols and olefins derived from further hydrogenation and manipulation, are important products for a multitude of industrial applications and processes. Stemming from this importance, the reaction has remained the subject of significant scientific efforts with advances continuing to be made.1b,3

View Article: PubMed Central - PubMed

ABSTRACT

Dehydroformylation, or the reaction of aldehydes to produce alkenes, hydrogen gas, and carbon monoxide, is a powerful transformation that is underdeveloped despite the high industrial importance of the reverse reaction, hydroformylation. Interestingly, nature routinely performs a related transformation, oxidative dehydroformylation, in the biosynthesis of cholesterol and related sterols under mild conditions using base-metal catalysts. In contrast, chemists have recently developed a non-oxidative dehydroformylation method; however, it requires high temperatures and a precious-metal catalyst. Careful study of both approaches has informed our efforts to design a base-metal catalyzed, mild dehydroformylation method that incorporates benefits from each while avoiding several of their respective disadvantages. Importantly, we show that cooperative base metal catalysis presents a powerful, mechanistically unique approach to reactions which are difficult to achieve using conventional catalyst design.

No MeSH data available.