Metal‐free and asymmetric: The first enantioselective diamination of styrenes simply requires a chiral hypervalent iodine(III) reagent as an oxidant and bismesylimide as a nitrogen source (see scheme, Ms=methanesulfonyl). The reaction proceeds under mild conditions and with high enantiomeric excess.

First evidence for the existence of free trifluoromethyl anion CF 3 À has been obtained. The 3D-caged potassium cation in [K(crypt-222)] + is inaccessible to CF 3 À ,t hus rendering it uncoordinated ("naked"). Ionic [K(crypt-222)] + CF 3 À has been characterized by single-crystal X-rayd iffraction, solution NMR spectroscopy, DFT calculations,a nd reactivity towarde lectrophiles.

First evidence for the existence of free trifluoromethyl anion CF3 (-) has been obtained. The 3D-caged potassium cation in [K(crypt-222)](+) is inaccessible to CF3 (-) , thus rendering it uncoordinated ("naked"). Ionic [K(crypt-222)](+) CF3 (-) has been characterized by single-crystal X-ray diffraction, solution NMR spectroscopy, DFT calculations, and reactivity toward electrophiles.

The C-X bond (X = Br, Cl) of α-haloketones is smoothly trifluoromethylated with the fluoroform-derived CuCF(3) reagent recently developed in our laboratories. This is the first nucleophilic α-trifluoromethylation reaction of carbonyl compounds and a rare example of CF(3)-C(sp(3)) coupling. The transformation employs only low-cost chemicals and cleanly occurs in up to 99% yield at room temperature, thereby providing an unprecedentedly easy entry to valuable 2,2,2-trifluoroethylketones.

Fluoroform-derived CuCF3 recently discovered in our group exhibits remarkably high reactivity toward aryl and heteroaryl halides, performing best in the absence of extra ligands. A broad variety of iodoarenes undergo smooth trifluoromethylation with the "ligandless" CuCF3 at 23-50 °C to give the corresponding benzotrifluorides in nearly quantitative yield. A number of much less reactive aromatic bromides also have been trifluoromethylated, including pyridine, pyrimidine, pyrazine, and thiazole derivatives as well as aryl bromides bearing electron-withdrawing groups and/or ortho substituents. Only the most electrophilic chloroarenes can be trifluoromethylated, e.g., 2-chloronicotinic acid. Exceptionally high chemoselectivity of the reactions (no side-formation of arenes, biaryls, and C2F5 derivatives) has allowed for the isolation of a large number of trifluoromethylated products in high yield on a gram scale (up to 20 mmol). The CuCF3 reagent is destabilized by CuX coproduced in the reaction, the magnitude of the effect paralleling the Lewis acidity of CuX: CuCl > CuBr > CuI. While S(N)Ar and S(RN)1 mechanisms are not operational, there is a well-pronounced ortho effect, i.e., the enhanced reactivity of ortho-substituted aryl halides 2-RC6H4X toward CuCF3. Intriguingly, this ortho-effect is observed for R = NO2, COOH, CHO, COOEt, COCH3, OCH3, and even CH3, but not for R = CN. The fluoroform-derived CuCF3 reagent and its reactions with haloarenes provide an unmatched combination of reactivity, selectivity, and low cost.