Controlling Stereoselectivity with Noncovalent Interactions in Chiral Phosphoric Acid Organocatalysis

Chemical Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: March 18, 2025

Chiral phosphoric acids (CPAs) have emerged as highly effective Brønsted acid catalysts in an expanding range of asymmetric transformations, often through novel multifunctional substrate activation modes. Versatile and broadly appealing, these benefit from modular tunable structures, compatibility with additives. Given the unique types noncovalent interactions (NCIs) that can be established between CPAs various reactants─such hydrogen bonding, aromatic interactions, van der Waals forces─it is unsurprising catalyst systems become a promising approach for accessing diverse chiral product outcomes. This review aims to provide in-depth exploration mechanisms by which impart stereoselectivity, positioning NCIs central feature connects broad spectrum catalytic reactions. Spanning literature 2004 2024, it covers nucleophilic additions, radical atroposelective bond formations, highlighting applicability CPA organocatalysis. Special emphasis placed on structural mechanistic features govern CPA-substrate well tools techniques developed enhance our understanding their behavior. In addition emphasizing details stereocontrolling elements individual reactions, we carefully structured this natural progression specifics broader, class-level perspective. Overall, findings underscore critical role catalysis significant contributions advancing synthesis.

Language: Английский

Manganese‐ Mediated Cascade Radical Oxidative Cyclization/1,6‐Conjugate Addition of Unsaturated Oximes with p‐Quinone methides: Facile Access to β,β‐Diarylmethine Isoxazolines

Chemistry - An Asian Journal, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 9, 2024

A simple and efficient strategy for the synthesis of structurally diverse β,β-diarylmethine substituted isoxazoline derivatives have been developed. This approach employs a manganese-promoted oxidative cyclization coupled with 1,6-conjugate addition unsaturated oximes to p-quinone methides. The key features this study include formation C-O C-C bonds through intramolecular intermolecular interactions, facilitated by in situ generated iminoxyl radicals. isoxazolines, bearing wide range functional groups, were isolated high yields.

Language: Английский