The H₈BINOL-based perfluoroalkyl ketone (S)-2 is found to exhibit highly enantioselective fluorescent enhancements toward both unfunctionalized and functionalized chiral amines. It greatly expands the substrate scope of the corresponding BINOL-based sensor. A dramatic solvent effect was observed for the reaction of the amines with compound (S)-2. In DMF, cleavage of the perfluoroalkyl group of compound (S)-2 to form amides was observed but not in other solvents, such as methylene chloride, chloroform, THF, hexane, and perfluorohexane. Thus, the addition of another solvent, such as THF, can effectively quench the reaction of compound (S)-2 with amines in DMF to allow stable fluorescent measurement. This is the first example that the formation of strong amide bonds under very mild conditions is used for the enantioselective recognition of chiral amines. The mechanism of the reaction of compound (S)-2 with chiral amines is investigated by using various analytical methods including mass spectrometry as well as NMR and UV/Vis absorption spectroscopy.

P450 119 peroxygenase and its site-directed mutants are discovered to catalyze the enantioselective epoxidation of methyl-substituted styrenes. Two new site-directed P450 119 mutants, namely T213Y and T213M, which were designed to improve the enantioselectivity and activity for the epoxidation of styrene and its methyl substituted derivatives, were studied. The T213M mutant is found to be the first engineered P450 peroxygenase that shows highly enantioselective epoxidation of cis-β-methylstyrenes, with up to 91 % ee. Molecular modeling studies provide insights into the different catalytic activity of the T213M mutant and the T213Y mutant in the epoxidation of cis-β-methylstyrene. The results of the calculations also contribute to a better understanding of the substrate specificity and configuration control for the regio- and stereoselective peroxygenation catalyzed by the T213M mutant.

A 1,1′-bi-2-naphthol (BINOL)-based chiral aldehyde in combination with Zn^II shows a highly enantioselective fluorescent response toward functional chiral amines at λ>500 nm. However, the combination of salicylaldehyde and Zn^II gives the same fluorescent enhancement for both enantiomers of a functional chiral amine at λ=447 nm. By using the fluorescent responses of the combination of the BINOL-based chiral aldehyde, salicylaldehyde and Zn^II at the two emission wavelengths, both the concentration and enantiomeric composition of functional chiral amines such as amino alcohols, diamines, and amino acids can be simultaneously determined by a single fluorescent measurement. This work provides a simple and convenient method for chiral assay.

Chiral propargylic ether-based triene–ynes are synthesized with high enantiomeric purity by employing an asymmetric enyne addition to aldehydes catalyzed by 1,1′-bi-2-naphthol in combination with ZnEt₂, Ti(OiPr)₄ and dicyclohexylamine at room temperature. These substrates are found to undergo a one-pot domino Pauson–Khand and Diels–Alder cycloaddition catalyzed by [RhCl(CO)₂]₂ under CO to generate a series of multicyclic products with high chemoselectivity and stereoselectivity. These products contain the multicyclic core structure of mangicol A which could facilitate the synthesis and study of this class of natural products.