Enantioselective Dynamic Exchange Reactions of Imines

• Published in: Journal of organic chemistry Vol. 86; no. 18; pp. 12932 - 12944
• Main Authors: Ji, Rui-Xue, Liu, Ning, Shen, Jiang-Shan
• Format: Journal Article
• Language: English
• Published: American Chemical Society 17-09-2021
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/acs.joc.1c01620

Although dynamic reactions of imines have been extensively studied, the dynamic behaviors manipulated by chirality remain nearly unexplored. In this work, enantioselective amine exchange reactions were demonstrated as a first example via the reaction of enantiomeric chiral amines such as natural amino acids with a series of innovative axially chiral 1,1′-binaphthyl-2,2′-diamine (BNDA)-based imines that were prepared from the condensation reactions between BNDA and salicylaldehyde (SA) or its derivatives. This enantioselective dynamic behavior can be directly indicated by the degree of the fluorescence response of the R-configuration of imines to the d-enantiomer of chiral amine, because the released BNDA can serve as the fluorescence signal output when the amine exchange reaction occurs, which is far higher than the response to its l-enantiomer under identical experimental conditions. For the S-configuration of chiral imines, the fluorescence response is the opposite. The enantioselective exchange reaction can be tuned by altering the electron-withdrawing or electron-donating capability of the substituent at position 4 or 5 of the SA part of chiral imines. Not only o-OH groups in SA-based imines but also protic solvents used as reaction media were found to be important to the dynamic behavior at high rates.