Non-Canonical Catalytic Asymmetric Reactions: Reflexive Chirality Transfer & Extraordinary Remote Enantioinduction

 

Non-Canonical Catalytic Asymmetric Reactions: Reflexive Chirality Transfer & Extraordinary Remote Enantioinduction

 

Date: 21^stNovember, 2025 (Friday)

Time: 10:45 - 11:45 am (HKT)

 

Venue: Lecture Theatre 102, K.K. Leung Building

 

 

Faculty of Pharmaceutical Sciences 

Hokkaido University

 

1. Reflexive Chirality Transfer (RCT)¹: In conventional enolate chemistry, α-carbon chirality is lost, requiring external chiral sources to afford optically active products, even starting with optically active substrates. We have overturned this paradigm with a strategy termed “reflexive chirality transfer (RCT)”. In RCT process, optically active α-amino acid derivatives are directly converted into optically active α-tetrasubstituted products with preserving their chirality. The chirality the α-carbon is transiently preserved as metal-centered chirality in the enolate and reinstated in the product. The RCT process offers a simple and cost-effective route to optically active molecules, overcoming the limitations of chiral pool synthesis.

 

2. Extraordinary Remote Enantioinduction²: Remote asymmetric induction remains a significant challenge because its efficiency dramatically decreases as the distance between the reacting site and the prochiral center increases, especially in flexible substrates. We have addressed this problem by designing chiral dirhodium catalysts bearing a nano-scale chiral deep pocket that direct enantioselective C–H amination at positions distal to the prochiral center. These catalysts enabled unprecedented desymmetrization of flexible 1,7-bisarenes and prochiral rotaxanes via chemo- and regioselective C–H amination, providing a new strategy for remote asymmetric induction.

 

1. Morisaki, K.; Furuki, Y.; Kousaka, R.; Nagai, S.; Oonishi, Y. Sato, Y. J. Am. Chem. Soc. 2025, 147, 12740.

2. Morisaki, K.; Emi, R.; Sato, Y.; Chen, G.; Ueda, Y.; Kawabata, T. submitted