10.1002/anie.200700165
The research explores a new and practical method for synthesizing enantiopure 1,2-diarylaziridines, which are significant in natural products and have potential applications as pesticides with low mammalian toxicity. The study leverages the enantioselective reductive amination of α-chloroketones using trichlorosilane (Cl3SiH) catalyzed by formamides derived from L-valine. Trichlorosilane (Cl3SiH) plays a crucial role as the reducing agent for the enantioselective reductive amination of α-chloroketones. It is used to selectively reduce α-chloroimines to α-chloroamines, which are then cyclized to form the desired aziridines. The use of trichlorosilane in this context is innovative because it allows for high enantioselectivity (up to 96% ee) in the reduction step, which is catalyzed by formamides derived from L-valine. This reduction process is key to achieving the enantiopure α-chloroamines that are essential for the subsequent synthesis of enantiopure 1,2-diarylaziridines. The study highlights the efficiency and selectivity of trichlorosilane in this catalytic reduction, contributing to the overall practicality and novelty of the synthetic method described. It successfully synthesizes 1,2-diarylaziridines as pure enantiomers for the first time, overcoming previous challenges in enantioselective synthesis of these compounds.
10.1039/c9ra01180c
The research focuses on the enantioselective conjugate hydrosilylation of β,β-disubstituted α,β-unsaturated ketones, utilizing chiral picolinamide–sulfonate Lewis base catalysts. The main objective was to synthesize various chiral ketones with a chiral center at the β-position, which are crucial intermediates for natural products and chiral drugs. The experiments involved screening different chiral Lewis base catalysts for the hydrosilylation of (E)-1,3-diphenylbut-2-en-1-one in acetonitrile at 0°C, and optimizing reaction conditions such as solvents and temperature to achieve the best yield and enantioselectivity. The reactants included α,β-unsaturated ketones, trichlorosilane, and the selected catalyst 2f. The analyses used to determine the success of the reactions and the enantiomeric excess (ee) of the products were chiral high-performance liquid chromatography (HPLC) and nuclear magnetic resonance (NMR) spectroscopy.