Benzoin Reaction

Langdon, Steven M.; Parmar, Karnjit; Wilde, Myron M. D.; Gravel, Michel

doi:10.1002/9783527809042.ch2

Cited by 2 publications

(2 citation statements)

References 95 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…N-Heterocyclic carbenes in recent decades have been catapulted into the chemical limelight as privileged organocatalysts with extensive utility for stitching together diverse molecular scaffolds, expanding the 3D chemical space . In this vein, imidazolinylidine, triazolylidene, and thiazolylidene NHCs (Figure a) continue to attract tremendous interest from the chemical community for applications such as carbon–carbon bond-forming reactions of aldehydes, Michael acceptors, and aldimines to formal redox transformations of aldehydes bearing R-reducible functionalities and beyond.…”

Section: Introductionmentioning

confidence: 99%

N-Heterocyclic Carbene Organocatalyzed Redox-Active/Ring Expansion Reactions: Mechanistic Insights Unveiling Base Cooperativity

2022

Self Cite

View full text Add to dashboard Cite

N-Heterocyclic carbene (NHC) organocatalyzed transformations of redox-active chemical manifolds is a powerful strategy for interconverting and expanding the chemical space. This approach in the context of ring expansion holds promise for preparing lactones from plentiful redox active aldehydes, despite a lack of rigorous mechanistic insights into the underlying elements governing this reactivity and with-it relevance to other NHC organocatalyzed transformations. Herein, in investigating this reactivity under the lens of modern day quantum mechanical calculations, we explore the mechanism of redox-active/ring expansion reactions of aldehydes furnishing lactone products by means of NHC organocatalysis. Through this comprehensive study, the underpinning mechanism of Breslow intermediate formation and ensuing downstream processes such as intermolecular C–C bond formation providing benzoin products versus intramolecular redox pathways are outlined. Notably, this study of NHC organocatalysis reveals the diverse role of bases as cooperative agents in directing and selectively routing reactivity, as highlighted here toward ring expanded lactone products.

show abstract

Section: Introductionmentioning

confidence: 99%

N-Heterocyclic Carbene Organocatalyzed Redox-Active/Ring Expansion Reactions: Mechanistic Insights Unveiling Base Cooperativity

2022

Self Cite

View full text Add to dashboard Cite

show abstract

“…Benzoin condensation is a carbon–carbon bond-forming reaction between two aldehyde molecules to furnish an α-hydroxyketone motif . It is a representative example of an umpolung reaction, in which the polarity of a carbonyl group is inverted through the catalytic action of a cyanide ion or an N -heterocyclic carbene (NHC).…”

mentioning

confidence: 99%

Selective Synthesis of Acylated Cross-Benzoins from Acylals and Aldehydes via N-Heterocyclic Carbene Catalysis

2021

View full text Add to dashboard Cite

The utility of acylals as building blocks for selective cross-benzoin synthesis was explored in this study. The synthesis of α-acetoxyketones (O-acyl cross-benzoins) was achieved via selective N-heterocyclic carbene-catalyzed cross-benzoin reactions using acylals as aldehyde equivalents. Thus, the combination of ortho-substituted phenyl acylals and aromatic/aliphatic aldehydes as coupling substrates using bicyclic triazolium salts as precatalysts and potassium carbonate as a base in THF at reflux temperature selectively yielded O-acyl cross-benzoins.

show abstract

Benzoin Reaction

Cited by 2 publications

References 95 publications

N-Heterocyclic Carbene Organocatalyzed Redox-Active/Ring Expansion Reactions: Mechanistic Insights Unveiling Base Cooperativity

N-Heterocyclic Carbene Organocatalyzed Redox-Active/Ring Expansion Reactions: Mechanistic Insights Unveiling Base Cooperativity

Selective Synthesis of Acylated Cross-Benzoins from Acylals and Aldehydes via N-Heterocyclic Carbene Catalysis

Contact Info

Product

Resources

About