Determination of the Absolute Configuration of (S)-N-(1-Aryl-allyl)-3,5-dinitrobenzamides and Their Elution Order on Brush-Type Chiral Stationary Phases

• Published in: European Journal of Organic Chemistry
• Main Authors: Knežević, Anamarija, Novak, Jurica, Pescitelli, Gennaro, Vinković, Vladimir
• Format: Article in Journal/Newspaper
• Language: English
• Published: 2018
• Subjects: Ab initio calculation; Chiral resolution; Circular dichroism; Configuration determination; Liquid chromatography; Physical and Theoretical Chemistry; Organic Chemistry; Antarc*; Antarctica
• Online Access: http://hdl.handle.net/11568/938667; https://doi.org/10.1002/ejoc.201800346; https://onlinelibrary.wiley.com/doi/full/10.1002/ejoc.201800346

A series of ten enantiomerically pure (S)-N-(1-aryl-allyl)-3,5-dinitrobenzamides (S-DNBs) was prepared using enzymatic resolution and chiral chromatography. Enzymatic resolution of corresponding 1-aryl-allylamines using Candida antarctica lipase B (CaLB) was efficient for amines with no steric hindrance near the stereogenic center and S-DNB amides were prepared by acylation of the obtained S-amine. When steric effects interrupted enzymatic resolution, racemic DNB amides were resolved using a brush-type chiral column (CSP-A) developed in our laboratory. Previously reported behavior of CaLB in kinetic resolution of amines was considered a starting point for the determination of absolute configuration (AC). The AC of prepared S-DNB amides was anticipated using the elution order of prepared DNB amides on CSP-A and commercial Whelk-O1 columns and comparison with DNB amides obtained after acylation of (S)-amines. The comparison between experimental electronic circular dichroism (ECD) spectra with those obtained by conformational analysis and ECD calculations of representative compounds allowed us to verify the AC of prepared DNB amides.