434-45-7Relevant articles and documents
Ion-Molecule Reactions in Gaseous CF4/CO Mixtures. Formation and Reactivity of CF3CO(1+) Ions
Cacace, Fulvio,Crestoni, Maria Elisa,Fornarini, Simonetta
, p. 1641 - 1647 (1994)
The reactivity of CF3CO(1+) ions, formed via two different routes, has been studied in the gas phase by the joint use of mass spectrometric and radiolytic techniques, spanning a pressure range from 10-8 Torr to ca. 1 atm.The 23 kcal mol-1 exothermic addition of CF3(1+) to CO provides a route to CF3CO(1+) requiring third-body stabilization of the adduct ion.In the 10-8 Torr pressure regime of Fourier transform ion cyclotron resonance (FT-ICR) spectrometry, CF3CO(1+) ions from electron ionization (EI) induced fragmentation of trifluoroacetic anhydride yield NuCF3(1+) products from oxygen-centered nucleophiles (Nu) and XC6H4CO(1+) ions from aromatics (C6H5X).At ca. 1 atm trifluoroacetylated products are efficiently formed even with strongly deactivated aromatics, showing distinct intra- and intermolecular selectivity features pertaining to the reactant CF3CO(1+) ions.The reactivity pattern is interpreted according to a kinetic interplay of collisional and chemical events depending on the activation of C6H5X toward electrophilic attack.
CARBON-14 KINETIC ISOTOPE EFFECTS AND MECHANISM IN THE SOLVOLYSIS OF 1,1,1-TRIFLUORO-2-PHENYL-2-PROPYL-3-14C p-TOLUENESULFONATE
Guo, Zili,Fry, Arthur
, p. 5059 - 5062 (1986)
In the solvolysis of 1,1,1-trifluoro-2-phenyl-2-propyl-3-14C p-toluenesulfonate there is only a small βC isotope effect, k/βk = 1.008+/-0.002.The result is as expected for a branching SN1/E1 reaction (mostly SN1).This is the first example of such a measurement.
Decarbonylative Fluoroalkylation at Palladium(II): From Fundamental Organometallic Studies to Catalysis
Lalloo, Naish,Malapit, Christian A.,Taimoory, S. Maryamdokht,Brigham, Conor E.,Sanford, Melanie S.
supporting information, p. 18617 - 18625 (2021/11/16)
This Article describes the development of a decarbonylative Pd-catalyzed aryl-fluoroalkyl bond-forming reaction that couples fluoroalkylcarboxylic acid-derived electrophiles [RFC(O)X] with aryl organometallics (Ar-M′). This reaction was optimized by interrogating the individual steps of the catalytic cycle (oxidative addition, carbonyl de-insertion, transmetalation, and reductive elimination) to identify a compatible pair of coupling partners and an appropriate Pd catalyst. These stoichiometric organometallic studies revealed several critical elements for reaction design. First, uncatalyzed background reactions between RFC(O)X and Ar-M′ can be avoided by using M′ = boronate ester. Second, carbonyl de-insertion and Ar-RF reductive elimination are the two slowest steps of the catalytic cycle when RF = CF3. Both steps are dramatically accelerated upon changing to RF = CHF2. Computational studies reveal that a favorable F2C-H - -X interaction contributes to accelerating carbonyl de-insertion in this system. Finally, transmetalation is slow with X = difluoroacetate but fast with X = F. Ultimately, these studies enabled the development of an (SPhos)Pd-catalyzed decarbonylative difluoromethylation of aryl neopentylglycol boronate esters with difluoroacetyl fluoride.
Decarboxylative Amination: Diazirines as Single and Double Electrophilic Nitrogen Transfer Reagents
Chandrachud, Preeti P.,Wojtas, Lukasz,Lopchuk, Justin M.
supporting information, p. 21743 - 21750 (2021/01/11)
The ubiquity of nitrogen-containing small molecules in medicine necessitates the continued search for improved methods for C-N bond formation. Electrophilic amination often requires a disparate toolkit of reagents whose selection depends on the specific structure and functionality of the substrate to be aminated. Further, many of these reagents are challenging to handle, engage in undesired side reactions, and function only within a narrow scope. Here we report the use of diazirines as practical reagents for the decarboxylative amination of simple and complex redox-active esters. The diaziridines thus produced are readily diversifiable to amines, hydrazines, and nitrogen-containing heterocycles in one step. The reaction has also been applied in fluorous phase synthesis with a perfluorinated diazirine.