Chiral Induction and Remote Chiral Communication in Quinoline Oligoamide Foldamers for Determination of Enantiomeric Excess and Absolute Configuration of Chiral Amines and Their Derivatives. Issue 62 (9th October 2019)

• Record Type: Journal Article
• Authors: Zheng, Lu; Zhan, Yulin; Ye, Lin; Zheng, Dan; Wang, Ying; Zhang, Kun; Jiang, Hua
• Is Part Of: Chemistry. Volume 25:Issue 62(2019)
• Page Start: 14162
• Page End: 14168
• Publication Date: 2019-10-09
• Subjects: chirality -- chiral induction -- circular dichroism -- configuration determination -- helical structures -- noncovalent interactions; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201903032
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: Two pentameric foldamers, Q5 and Q5C‐ S, containing a C−F bond were synthesized based on quinoline oligamide foldamers for the measurement of enantiomeric excess and for the determination of absolute configuration of chiral amines, diamines, amino alcohols, and α‐amino acid esters. Chiral induction of Q5 was triggered in situ when the chiral analytes reacted with the C−F bond in Q5 by a N‐nucleophilic substitution reaction, leading to a linear correlation between the CD amplitude at the region of quinoline chromophores and the ee values of the chiral analytes, which can be used for the ee determination of chiral analytes. Furthermore, the CD intensity of Q5C‐ S containing a chiral motif at its C‐terminus enhances via remote, favorable chiral communication when the chiral induction was triggered in situ by chiral analytes at the N‐terminus matches the original helicity of Q5C‐ S, but decreases via remote, conflicted chiral communication when the chiral induction is triggered in situ by chiral molecules at the N‐terminus mismatches the original one. The system can thus be used for determination of the absolute configuration of chiral analytes, given that the chirality of the chiral motif at the C‐terminus of Q5C‐ S is known. Abstract : Communicating chirality : A method is reported with which to measure the enantiomeric excess and absolute configuration of amines and their derivatives based on an efficient N‐nucleophilic substitution reaction via C−F bond cleavage and chiral induction or remote chiral communication of the quinolone oligoamide foldamers (see figure). This method has several advantages, including wide analyte scope and tolerance of air and water.