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.
Catalytic AgF-Initiated Intramolecular 1,3-Sulfonyl Migration of gem-Difluorovinyl Sulfonates to α,α-Difluoro-β-ketosulfones
Chen, Lei,Li, Xiong,Li, Yue,Lian, Zhong,Sun, Haotian,Xiong, Baojian,Xu, Jie
supporting information, p. 9263 - 9268 (2020/11/30)
A 1,3-sulfonyl migration of difluorovinyl sulfonates initiated by a catalytic amount of silver fluoride is presented. α,α-Difluoro-β-ketosulfones were successfully prepared in excellent yields. This method features high chemoselectivity, good functional group tolerance, high atom economy, and mild, environmentally benign reaction conditions. Furthermore, mechanistic experiments indicate that this migration proceeds in an intermolecular pathway and the corresponding sulfinates are possible intermediates.