Theoretical study on the nucleophilic fluoroalkylation of propylene oxide with fluorinated sulfones
نویسندگان
چکیده
The paths of nucleophilic fluoroalkylation reaction of propylene oxide with PhSO2CYF (Y = F, H, and PhSO2, respectively) in the gas phase and in Et2O solvent were studied theoretically. The nucleophilic fluoroalkylation of propylene oxide with fluorinated carbanions was probed by comparison of the reactivities (phenylsulfonyl)monofluoromethyl anion (PhSO2CHF), the (phenylsulfonyl)difluoromethyl anion (PhSO2CF2), and the bis(phenylsulfonyl)monofluoromethyl anion ((PhSO2)2CF). The nucleophilicity reactivity order of PhSO2CYF (Y = F, H, and PhSO2) is (PhSO2)2CF > PhSO2CHF > > PhSO2CF2, which indicates that the introduction of another electron-withdrawing phenylsulfonyl group is an effective way to significantly increase the nucleophilicity of fluorinated carbanions. For comparison, the nucleophilic addition reaction of propylene oxide with the chlorine-substituted carbanion PhSO2CHCl was investigated. The calculated results show that the nucleophilicity of PhSO2CYF is better than that of PhSO2CHCl in the ring opening reaction with propylene oxide. The calculated results are in good agreement with the available experimental ones.
منابع مشابه
Radical Fluoroalkylation of Isocyanides with Fluorinated Sulfones by Visible-Light Photoredox Catalysis.
The radical fluoroalkylation of isocyanides with fluorinated sulfones is enabled by visible-light photoredox catalysis. A wide range of readily available mono-, di-, and trifluoromethyl heteroaryl sulfones can thus be used as efficient radical fluoroalkylation reagents under mild conditions. This method not only describes a new synthetic application of fluorinated sulfones, but also provides a ...
متن کاملDIAD-mediated metal-free cross dehydrogenative coupling between tertiary amines and a-fluorinated sulfones†
Fluorinated amines, especially b-fluorinated amines, have received much attention in bioorganic and medicinal chemistry research due to the profound change of the basicity of the amine functionality imparted by fluorine substitution, which has dramatic and beneficial influences on the bioavailability of a target molecule. Among various methods for synthesizing fluorinated amines, nucleophilic f...
متن کاملCopper-mediated fluoroalkylation of aryl iodides enables facile access to diverse fluorinated compounds: the important role of the (2-pyridyl)sulfonyl group.
The (2-pyridyl)sulfonyl group was found to be a multifunctional group in the preparation of structurally diverse fluorinated products. It not only facilitates the copper-mediated (or catalyzed) cross-coupling reaction between α-fluoro sulfone 4a and aryl iodides, but also enables further transformations of the coupling products 2.
متن کاملNucleophilic fluoroalkylation/cyclization route to fluorinated phthalides
Discribed in this article is a versatile and practical method for the synthesis of C3-perfluoroalkyl-substituted phthalides in a one-pot manner. Upon treatment of KF or triethylamine, 2-cyanobenzaldehyde reacted with (perfluoroalkyl)trimethylsilanes via nucleophilic addition and subsequent intramolecular cyclization to give perfluoroalkylphthalides in good yields.
متن کاملElectrophilic trifluoromethylselenolation of terminal alkynes with Se-(trifluoromethyl) 4-methylbenzenesulfonoselenoate
Herein the nucleophilic addition of Se-(trifluoromethyl) 4-methylbenzenesulfonoselenoate, a stable and easy-to-handle reagent, to alkynes is described. This reaction provides trifluoromethylselenylated vinyl sulfones with good results and the method was extended also to higher fluorinated homologs. The obtained compounds are valuable building blocks for further syntheses of fluoroalkylselenolat...
متن کامل