101. Bis-tert-Alcohol-Functionalized Crown-6-Calix[4]arene: An Organic Promoter for Nucleophilic Fluorination
- Author
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Sungyul Lee, Dong Wook Kim, Sung-Sik Lee, Wonsil Choi, and Vinod H. Jadhav
- Subjects
Halogenation ,Hydrocarbons, Fluorinated ,Stereochemistry ,Alcohol ,010402 general chemistry ,01 natural sciences ,Medicinal chemistry ,Catalysis ,Phosphates ,Metal ,chemistry.chemical_compound ,Fluorides ,Nucleophile ,Cations ,Crown Ethers ,Calixarene ,Sulfhydryl Compounds ,Ethanol ,Molecular Structure ,010405 organic chemistry ,Hydrogen bond ,Organic Chemistry ,Hydrogen Bonding ,General Chemistry ,Alkali metal ,0104 chemical sciences ,chemistry ,Metals ,visual_art ,Alcohols ,visual_art.visual_art_medium ,SN2 reaction ,Calixarenes ,Fluoride - Abstract
A bis-tert-alcohol-functionalized crown-6-calix[4]arene (BACCA) was designed and prepared as a multifunctional organic promoter for nucleophilic fluorinations with CsF. By formation of a CsF/BACCA complex, BACCA could release a significantly active and selective fluoride source for SN2 fluorination reactions. The origin of the promoting effects of BACCA was studied by quantum chemical methods. The role of BACCA was revealed to be separation of the metal fluoride to a large distance (>8 A), thereby producing an essentially "free" F(-). The synergistic actions of the crown-6-calix[4]arene subunit (whose O atoms coordinate the counter-cation Cs(+)) and the terminal tert-alcohol OH groups (forming controlled hydrogen bonds with F(-)) of BACCA led to tremendous efficiency in SN2 fluorination of base-sensitive substrates.
- Published
- 2015