Stereochemical Communication within a Chiral Ion Pair Catalyst1. Issue 30 (23rd June 2015)

• Record Type: Journal Article
• Authors: Merten, Christian; Pollok, Corina H.; Liao, Saihu; List, Benjamin
• Is Part Of: Angewandte Chemie international edition. Volume 54:Issue 30(2015)
• Page Start: 8841
• Page End: 8845
• Publication Date: 2015-06-23
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201501271
• Languages: English
• ISSNs: 1433-7851

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>Ionic interactions are increasingly appreciated as a key, asymmetry‐inducing factor in enantioselective catalytic transformations, including those involving Brønsted acid or base catalysis, phase‐transfer catalysis, and related processes. However, a detailed understanding of these interactions is often lacking. Herein, we show how an enantiopure anion enforces a chiral conformation onto a catalytically relevant achiral cation. Specifically, we use vibrational circular dichroism (VCD) spectroscopy to monitor the transmission of stereochemical information from a chiral phosphate anion to a flexible manganese(III)–salen cation. We show that VCD can be used to study solvent effects and that the obtained chiroptical data directly and quantitatively correlate with the experimentally observed enantioselectivity in an asymmetric olefin epoxidation reaction.</p> </abstract>