Organic Lewis Acid Catalysis

Evolution of the Lewis acid catalysts developed in our group and presentation of the general catalytic cycle of asymmetric counteranion-directed Lewis acid catalysis. Shows molecular structures and a schematic catalytic cycle.

Extending the ACDC concept to silylium-based Lewis acid organocatalysts offers a distinctive and general solution for mitigating the detrimental achiral background catalysis frequently encountered with conventional metal-based catalyst systems. In 2009, we demonstrated that our chiral disulfonimides (DSIs) are not only strong Brønsted acids but also form active Lewis acids upon silylation. A significant advancement in the field of (organic) Lewis acid catalysis was the development of highly acidic, confined imidodiphosphorimidate (IDPi) organocatalysts in 2016. Thanks to their enzyme-like microenvironment, silylated IDPi catalysts are extremely reactive Lewis acids that achieve excellent stereocontrol, even at very low catalyst loadings approaching sub-ppm levels. Over the past decade, these in situ-generated Lewis acid organocatalysts have overcome previous limitations and provided elegant solutions to a number of long-standing challenges in the field.

Chemical reaction scheme with chiral counteranion catalysts and yields.

A Powerful Chiral Counteranion Motif for Asymmetric Catalysis
Chemical diagram showing Diels-Alder reactions catalyzed by silylated C-H acids, indicating yield and conditions.

Asymmetric Lewis acid organocatalysis of the Diels–Alder reaction by a silylated C–H acid
Diagram showing development of IDPi catalysts for Hosomi-Sakurai reaction with yield percentages.

Extremely Active Organocatalysts Enable a Highly Enantioselective Addition of Allyltrimethylsilane to Aldehydes
Diagram illustrating sub-ppm asymmetric organocatalysis with yield data.

Approaching sub-ppm-level asymmetric organocatalysis of a highly challenging and scalable carbon–carbon bond forming reaction
Diagram of catalytic Diels-Alder reaction, showing structures and reaction conditions, with yields up to 99%.

Scalable and Highly Diastereo- and Enantioselective Catalytic Diels–Alder Reaction of α,β-Unsaturated Methyl Esters
Diagram showing asymmetric aldolization with acetaldehyde enolates, including molecular structures and yields.

Confined acids catalyze asymmetric single aldolizations of acetaldehyde enolates
Diagram showcasing azine activation using silyl catalysis, featuring molecular structures and chemical equations.

Azine Activation via Silylium Catalysis
Diagram illustrating confinement-controlled selective catalytic asymmetric Mukaiyama aldolizations with chemical structures.

Confinement-Controlled, Either syn- or anti-Selective Catalytic Asymmetric Mukaiyama Aldolizations of Propionaldehyde Enolsilanes
Flowchart illustrating catalytic approach for β3-amino acid synthesis with excellent enantioselectivity.

Harnessing the ambiphilicity of silyl nitronates in a catalytic asymmetric approach to aliphatic β3-amino acids
Diagram showing steps for synthesizing Remdesivir nucleoside with yields.

Direct and Catalytic C-Glycosylation of Arenes: Expeditious Synthesis of the Remdesivir Nucleoside
Diagram illustrating organocatalytic stereoselective cyanation of ketones with yields and conditions.

Organocatalytic stereoselective cyanosilylation of small ketones
Chemical process diagram illustrating pericyclic umpolung in a Diels-Alder reaction involving tropone and enol ethers.

Pericyclic Umpolung in a Catalytic Asymmetric Diels–Alder Reaction of Tropone with Enol Ethers
Chemical synthesis diagram with various compounds and reactions.

The asymmetric synthesis of an acyclic N-stereogenic amine
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