Citation: QIN Xu-Long, HAN Fu-She. Study on Reaction Mechanism of Desymmetric Enantioselective Reduction of Cyclic 1,3-Diketones Aided by Gas Chromatography[J]. Chinese Journal of Analytical Chemistry, ;2022, 50(2): 290-299. doi: 10.19756/j.issn.0253-3820.211170 shu

Study on Reaction Mechanism of Desymmetric Enantioselective Reduction of Cyclic 1,3-Diketones Aided by Gas Chromatography

QIN Xu-Long ^1,2 ,
HAN Fu-She ^1,2,,

1.
Green Chemistry and Process Laboratory, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China;
2.
University of Science and Technology of China, Hefei 230026, China

Corresponding author: HAN Fu-She, fshan@ciac.ac.cn
Received Date: 9 March 2021
Revised Date: 4 May 2021

Fund Project: Supported by the National Natural Science Foundation of China (No.22071235)

A gas chromatography (GC) method was established for determination of conversion rate and product content in the desymmetric enantioselective reduction of 1,3-cyclopentadione compounds. This method could be used as a useful supplementary method to investigate the mechanism of desymmetric enantioselective reduction of cyclic 1,3-diketones catalyzed by chiral phosphonamides. The samples were separated on a DB-WAX column (30 m×0.25 mm, 0.25 μm) and analyzed qualitatively and quantitatively by gas chromatography using a standard compound comparison method. The method could be used for convenient, rapid and accurate determination of content of the remaining starting materials and different products generated at different reaction time. By using the established detection method, the reaction course under four different reaction conditions (without additive and catalyst, with additive only, with catalyst only and with both additive and catalyst) were monitored in detail. The results showed that the reaction with the concomitant presence of N,N-diisopropylethylamine (DIPEA) and catalyst not only proceeded much faster but also provided higher yields compared with other three reaction systems. Namely, the conversion rate was up to 80% within 5 min, and the content of target product was close to 70%. In addition, control experiments showed that the addition of DIPEA could also greatly improve the enantioselectivity of the product. Consequently, a combination of these results with our previous mechanistic study by using NMR method provided a further understanding of the mechanism of the related reactions, namely, the addition of amine additives could promote the formation of chiral catalytically active species.
- 1,3-Cyclopentanedione,
- Desymmetric reduction,
- Gas chromatography,
- Additives,
- Conversion rate
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