Determination of pK a Values of C-H Bonds in Polar Fluorinated Arenes Referred to a New CF 3 SO 2 -Substituted Anchor Compound.

Autor: Kong X; State Key Laboratory of Elemento-organic Chemistry, College of Chemistry, Nankai University, Weijin Road No. 94, Tianjin, 300071, China., Liang Y; State Key Laboratory of Elemento-organic Chemistry, College of Chemistry, Nankai University, Weijin Road No. 94, Tianjin, 300071, China., Guo Z; State Key Laboratory of Elemento-organic Chemistry, College of Chemistry, Nankai University, Weijin Road No. 94, Tianjin, 300071, China., Lin T; State Key Laboratory of Elemento-organic Chemistry, College of Chemistry, Nankai University, Weijin Road No. 94, Tianjin, 300071, China., Liu S; State Key Laboratory of Elemento-organic Chemistry, College of Chemistry, Nankai University, Weijin Road No. 94, Tianjin, 300071, China., Liu Z; State Key Laboratory of Elemento-organic Chemistry, College of Chemistry, Nankai University, Weijin Road No. 94, Tianjin, 300071, China., Liu T; State Key Laboratory of Elemento-organic Chemistry, College of Chemistry, Nankai University, Weijin Road No. 94, Tianjin, 300071, China.; Haihe Laboratory of Sustainable Chemical Transformations, Tianjin, 300192, China., Cheng JP; State Key Laboratory of Elemento-organic Chemistry, College of Chemistry, Nankai University, Weijin Road No. 94, Tianjin, 300071, China.; Haihe Laboratory of Sustainable Chemical Transformations, Tianjin, 300192, China.; Center of Basic Molecular Science, Department of Chemistry, Tsinghua University, Beijing, 100084, China.
Jazyk: angličtina
Zdroj: ChemSusChem [ChemSusChem] 2024 Nov 20, pp. e202402041. Date of Electronic Publication: 2024 Nov 20.
DOI: 10.1002/cssc.202402041
Abstrakt: pK a values of C-H bonds remain unreported and challenging in fluorous solvents because of these solvents' unique physicochemical properties, although they have been measured, theorized and predicted successfully in water and common organic solvents. Herein, a new CF 3 SO 2 -substituted anchor compound designed for matching the physicochemical properties of polar fluorinated arenes is synthesized. Its self-dissociation constants in these solvents are used as bases for experimentally determining the pK a values of 36 C-H compounds in them. These experimentally determined pK a values exhibit excellent linear free-energy relationships and correlate well with their corresponding DFT-calculated values. These data indicate that the polar fluorinated arenes are thermodynamically more favorable for deprotonation of ketone derivatives than acetonitrile as reaction media, resulting in enhanced deprotonation-promoted CO 2 fixation. The pK a values determined in this work can be used as an important guidance tool for reactions involving the formation and cleavage of C-H bonds in polar fluorinated arenes.
(© 2024 Wiley-VCH GmbH.)
Databáze: MEDLINE
Externí odkaz: