Complexation And Enantioselectivity Of Asymmetric Sulfur/Selenium-Substituted Uranyl-Salophens For Chiral Morpholinols

Chirality is different,its corresponding biological,pharmacological and toxicological effects will be very different.And the selective synthesis or separation of chiral antidepressant morpholinol has always been a research hotspot and difficulty.In this paper,the selective recognition of the antidepressant RRS/SSR-3,5-dimethyl-2-?3-fluorophenyl?-2-morpholinolsbytheasymmetric sulfur/selenium-substituted uranyl-salophen was theoretical exploration.In recent years,the design,synthesis and applications of unilaterally substituted asymmetric uranyl-salophen complexes have become an extremely important research field.Among them,the recognition performance of asymmetric uranyl-salophen compounds has become a research focus in recent years.In this paper,the density functional theory?DFT?/M062X/6-311G**/RECP method level was used to explore the asymmetric sulfur/selenium-substituted uranyl-salophen containing R/S-chiral carbon substituents,we found there existence of two?/V-type diastereomers,and then used the two?/V-type diastereoisomers as receptors to coordinated the guests of 3,5-dimethyl-2-?3-fluorophenyl?-2-morpholinols with RRS/SSR configurations.The simulation calculations were performed on all the receptor molecules,guest molecules and Receptor-Guest complexes,and the geometric configuration,Wiberg bond order,the electron density difference maps,the localized orbital locator figures,front-line molecular orbital,infrared spectrum and binding energy were obtained and analyzed.The rules of enantioselective recognition of four chiral receptors of?/V-R/S for two chiral RRS/SSR-guests were presented.The results showed that because of the asymmetric substituent groups on the N₁ side of the asymmetric sulfur/selenium substituted uranyl-salophen,the bond lengths of U-N₁,U-S₁ and U-Se₁ were greater than U-N₂,U-S₂ and U-Se₂,respectively.While the Wiberg bond order of U-N₁,U-S₁ and U-Se₁ were smaller than U-N₂,U-S₂ and U-Se₂,respectively,and the coordination capacity of N₁,S₁ and Se₁ atoms with U atom was less than N₂,S₂ and Se₂.The geometric configuration,infrared spectrum,and Wiberg bond order of the diastereomers formed by the skeleton's reverse of asymmetric sulfur/selenium substituted uranyl-salophen differed little,but there was a certain difference in the enantioselective recognition for the enantiomeric guest molecules:under vacuum and solvents?water,acetone and toluene?,the?/V-R type asymmetric sulfur-substituted uranyl-salophen receptors had better enantioselectivity for enantiomeric guests than the?/V-S type receptors,and the?-R type receptor exhibited better enantioselectivity for the guests especially in the case of vacuum,water and toluene solvents.However,the?/V-R/S four selenium-substituted uranyl-salophen receptors had good enantioselective recognition for guest molecules in acetone solvent,and the?-R type receptor under acetone and vacuum had the best enantioselectivity for guest molecules.The first chapter of this article expounds the research background,and introduces the research object,innovation and research significance of this paper.The second chapter of this paper roughly introduces density functional theory and Gaussian16 and Multifwn calculation software.In Chapters 3 and 4 of this paper,the complexation and enantioselectivity of asymmetric sulfur or selenium substituted uranyl-salophen for chiral morpholinols are studied respectively.The fifth chapter is a summary and prospect of this article.