Work

Catalytic asymmetric construction of remote P or other heteroatom (Si/S) stereogenic axially chiral scaffolds

Year: 2025

Type: article

Abstract: Axial chirality represents a fundamental element of stereochemistry and is a defining structural feature in many chiral compounds. Although the axial chirality of atropisomers, allenes and spiranes has been extensively studied, the chemistry of alkylidenecycloalkanes and their analogues-especially those possessing P-, S- or Si-based axial chirality-remains underdeveloped. Here we report a chiral phosphoric acid-catalyzed oxime condensation that enables the construction of remote heteroatom (P/S/Si)-stereogenic axially chiral scaffolds. The reaction accommodates a broad range of functional groups, delivering optically active axially chiral 9-heteroanthrone-based oxime ethers in good to excellent enantioselectivities (up to 98 : 2 er). We also describe a modular synthesis of dibenzoazaphosphepinones and demonstrate their application as chiral monodentate phosphine ligands in asymmetric catalysis.

Source: Chemical Science

DOI: 10.1039/d5sc08143b

Authors: Wenqi Liu, Zhijie Ling, Yang-Zi Liu, Wei-Ping Deng

Institution: Zhejiang Normal University

Language: English

Topic: Axial and Atropisomeric Chirality Synthesis

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: diamond

Funder: National Natural Science Foundation of China

Award: G8988554920