Asymmetric Counteranion-Directed Catalysis (ACDC)

Diagram depicting ACDC, highlighting catalysis methods including amino, metal, photoredox, and others, with chemical structures and labels.

Since introducing the concept of asymmetric counteranion-directed catalysis (ACDC) in our studies on asymmetric transfer hydrogenations in 2006, we have continuously striven to apply the method to increasingly challenging chemical transformations. The realisation that any reaction involving a cationic intermediate can potentially be rendered enantioselective through ion pairing with an enantiopure counteranion has led to the development of numerous catalytic asymmetric transformations. Over the past two decades, the ACDC framework has evolved to encompass transition metals, Brønsted acids, silylium-Lewis acids, and most recently, photoredox catalysts.

Bronsted

Brønsted Acid Catalysis

Due to the vast number of reactions that can be catalyzed by Brønsted acids, a core area of our research focuses on the development and application of chiral organic Brønsted acids for asymmetric counteranion-directed catalysis (ACDC). To date...
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Organic Lewis Acid Catalysis

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. [more]
ACPC

Asymmetric Counteranion-Directed Photoredox Catalysis (ACPC)

Achieving high enantioselectivity in photoredox transformations poses a formidable challenge in asymmetric catalysis, possibly because of the high energy of the activated radical (ion) intermediates. Very recently, our group unlocked a new general reactivity mode of IDPi catalysts. Pairing of cationic photocatalysts with IDPi counteranions delivers chiral photoredox catalyst systems. [more]

Selected Publications

Diagram shows chemical structures and processes in asymmetric catalysis with TRIP morpholinium salt.

Asymmetric Counteranion-Directed Catalysis
Diagram of enantioselective palladium-catalyzed direct allylation of aldehydes, showing synthesis steps and yields.

Chiral Counteranions in Asymmetric Transition-Metal Catalysis:  Highly Enantioselective Pd/Brønsted Acid-Catalyzed Direct α-Allylation of Aldehydes
Illustration of ion pairing with chiral CPA counterion, showing manganese-salen epoxidation mechanism.

Asymmetric Counteranion-Directed Transition-Metal Catalysis: Enantioselective Epoxidation of Alkenes with Manganese(III) Salen Phosphate Complexes
Chemical process diagram illustrating asymmetric ketone catalysis with CO₂, resulting in (+)-Crinane.

Asymmetric Catalysis with CO2: The Direct α-Allylation of Ketones
Diagram showing molecular structures and catalyst used in asymmetric transfer reactions.

From Reagent to Catalyst: Dispersion-Driven Design of a General Asymmetric Transfer Hydrogenation Catalyst
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