Trifluoromethyl reaction + metal atoms

Although these methods did result in the preparation of a number of then new compounds, they are inherently limited by the fact that the amount of material afforded by a typical reaction is often only in the tens of milligrams range, which is ample for product characterization but insufficient for a reasonably thorough examination of the chemistry of the new compounds. Additionally, while metal atom reactions have been successfully utilized on the elements of groups 10-12 (see below), the synthesis, isolation, and characterization of trifluoromethyl derivatives of the elements from earlier periods of the periodic table is yet to be established. 

PerfluoroaUcyl cadmium compounds are also known. Bis(trifluoromethyl)cadmium has been prepared at -78 °C by cocondensing Cd atoms with -CFs radicals generated in a hexafluoroethane plasma (see Metal Vapor Synthesis of Transition Metal Compounds),and also by the unusual reaction of activated cadmium powder with difluorodihalomethanes, for example, CF2CI2, CF2Br2, or CF2BrCl, in DMF (equation 7). ... 

Catalysts (25) are the Lewis acid-Lewis base bifunctional catalysts in which Lewis acid-Al(III) moiety activates acyl iminium ion and the Lewis base (oxygen of phosphine oxide) does TMSCN, simultaneously (Scheme 5.7). Halogen atoms at the 6-position enhanced both yields and enantioselectivity in Reissert-type cyanation of the imino part of 26. However, the order for the activation is not parallel to the electronegativity of the halogen atoms and, moreover, the strong electron-withdrawing trifluoromethyl group provided unexpectedly the worst result for the activation [13]. It is not simple to explain this phenomenon only in terms of the increased Lewis acidity of the metal center. Trifluoromethylated BINOL-zirconium catalysts (28) for asymmetric hetero Diels-Alder reaction (Scheme 5.8) [14], trifluoromethylated arylphosphine-palladium catalyst (32) for asymmetric hydrosilylation (Scheme 5.9) [15], and fluorinated BINOL-zinc catalyst (35) for asymmetric phenylation (Scheme 5.10) [16] are known. 

Fluorobenzothiophene derivative 68 was prepared in 44 % yield starting from 4-(methylthio)-l-(trifluoromethyl)benzene 65 by double metallation with n-BuLi and subsequent reaction with CO2. The primary intramolecular cycUza-tion of 66 was anchimerically assisted by the carboxylate anion in ortho position and gave rise to a nucleophilic substitution of the fluorine atom by the SCH" anion. The resulting intermediate 67 aromatized after acidification into 3-fluorobenzo[b]thiophene 68 [40]. 

The reaction of 2,3,4,5-tetrakis(trifluoromethyl)(yclopenta-2,4-dien-l-one with tertiary phosphines results in nucleophilic attack by the phosphine at carbonyl ojgrgen to form zwitterionic adducts. Nucleophilic attack at carbonyl ojgrgen is also implicated in a phosphine-mediated addition of 1,2-dicarbonyl compounds to nitroso-electrophiles. The diphosphine l,l-bis(diphenylphosphino)methane has been shown to undergo redox reactions with o-quinones, forming phosphine oxides of type (104). An overview of the reactions of HNO (azanone) with metal porphyrins includes reference to O-atom abstraction by phosphines from HNO to form nitrite. ... 

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