Versatile Route to Arylated Fluoroalkyl Bromide Building Blocks

New difunctionalized and fluoroalkylated silyl reagents have been prepared that react with silver and copper salts to afford active catalysts that can be used to synthesize arylated fluoroalkyl bromide building blocks. It has been shown that the [(phen)­Ag­(CF₂)_<i>n</i>Br] intermediates are capable of transferring both the phenanthroline ligand and the fluoroalkyl bromide chain to copper iodide, eliminating the need for a preligated copper salt precursor. The methodology is compatible with various chain lengths of the fluoroalkyl halide functionality

Oxygen-Bound Trifluoromethoxide Complexes of Copper and Gold

Well-defined copper and gold complexes have been prepared which contain the shortest structurally characterized metal–oxygen bonds between transition metals and a trifluoromethoxide moiety. The trifluoromethoxide ligand is O-bound to both the copper and gold centers, with a copper–oxygen distance of 1.849(4) Å and a gold–oxygen distance of 2.058(4) Å. Density functional theory (DFT) calculations on all new trifluoromethoxy complexes were performed in order to obtain bond lengths and angles that are not influenced from any intermolecular contacts in the solid state and also to provide a first glimpse of the electronic features of this previously unknown ligand

Direct Difluoromethylation of Aryl Halides via Base Metal Catalysis at Room Temperature

A stable and isolable difluoro­methyl zinc reagent has been prepared through the reaction of ICF₂H with diethyl zinc and DMPU. This new zinc reagent is a free-flowing solid and can be used in combination with a nickel catalyst to difluoro­methylate aryl iodides, bromides, and triflates at room temperature. Such mild conditions for the catalytic difluoro­methylation of these substrates are unprecedented

Oxygen-Bound Trifluoromethoxide Complexes of Copper and Gold

Well-defined copper and gold complexes have been prepared which contain the shortest structurally characterized metal–oxygen bonds between transition metals and a trifluoromethoxide moiety. The trifluoromethoxide ligand is O-bound to both the copper and gold centers, with a copper–oxygen distance of 1.849(4) Å and a gold–oxygen distance of 2.058(4) Å. Density functional theory (DFT) calculations on all new trifluoromethoxy complexes were performed in order to obtain bond lengths and angles that are not influenced from any intermolecular contacts in the solid state and also to provide a first glimpse of the electronic features of this previously unknown ligand

Stepwise Conversion of a Platinum Dimethyl Complex to a Perfluorometallacyclobutane Derivative

In this report, we have demonstrated proof-in-principle that simple dimethyl metal complexes could be used to generate perfluorometallacyclobutane derivatives. With the new methodology, we have more than doubled the number of known perfluorometallacyclobutanes in the literature. We have also structurally characterized three platinum perfluorometallacyclobutanes and have described a unique transformation whereby one [Pt­(C₃F₆)] functionality is converted to [Pt­(C₃F₄O₂)]. The new methodology to prepare perfluorometallacyclobutanes also avoids the use of tetrafluoroethylene, which is becoming increasingly difficult to purchase due to the explosion hazards associated with its use

Nickel-Catalyzed Trifluoromethylselenolation of Aryl Halides Using the Readily Available [Me₄N][SeCF₃] Salt

A convenient and efficient method for the construction of aryl trifluoromethyl selenoethers from the corresponding aryl halides in the presence of Ni­(COD)₂ and an appropriate ligand is reported. Various aryl iodides, bromides, and chlorides were smoothly converted in this reaction by simply varying the ligand, which afforded aryl and heteroaryl trifluoromethyl selenoethers in good to almost quantitative yields. The reaction was also applicable to the synthesis of druglike molecules. This work is the first report for trifluoromethylselenolation of aryl chlorides. Advantages of the present Ni-catalyzed approach include mild reaction conditions, good functional group tolerance, inexpensive reagents, easy operation, and no use of additional additives. This protocol allows for a straightforward and reliable access to trifluoromethyl selenides that are latent screening candidates for new pharmaceuticals and agrochemicals

Manganese-Catalyzed Aerobic Oxytrifluoromethylation of Styrene Derivatives Using CF₃SO₂Na as the Trifluoromethyl Source

A mild and practical protocol for manganese-catalyzed aerobic oxytrifluoromethylation of olefinic bonds of styrene derivatives using CF₃SO₂Na (Langlois’ reagent) as the CF₃ source is described. A distinguishing feature of this method is the generation of trifluoromethyl radicals from CF₃SO₂Na using the simple manganese salt/O₂ system. The reaction proceeds under ambient conditions, free of added peroxide initiators, and provides moderate to good selectivities for alcohol versus ketone product

Linear Bis(perfluoroalkyl) Complexes of Nickel Bipyridine

Three new complexes were prepared: [(dtbpy)­Ni­(CF₃)₂] (<b>1</b>), [(dtbpy)­Ni­(CF₂CF₃)₂] (<b>2</b>), and [(dtbpy)­Ni­(CH₃)₂] (<b>3</b>) (dtbpy = 4,4′-di-<i>tert</i>-butyl-2,2′-bipyridine). Remarkable differences in the structure, electronics, reactivity, and absorption of visible light for the alkyl versus perfluoroalkyl complexes were observed and are detailed in this report

Nitrogen–Nitrogen Bond Formation via a Substrate-Bound Anion at a Mononuclear Nickel Platform

The nickel-C₄F₈ fragment coordinates an aminoaryl N–H ketimine to form a stable complex, which upon treatment with base and oxidant leads to an N–N bond-forming reaction and the release of indazole product. A key and previously unidentified intermediate in the formation of the indazole was a diimine complex of nickel bearing significant charge on the aryl ring that initially contained the amine substituent. The C₄F₈ coligand was key for the redox transformation and for stabilization of the intermediate for characterization

Mild, Safe, and Versatile Reagents for (CF₂)_<i>n</i> Transfer and the Construction of Fluoroalkyl-Containing Rings

The preparation of new dizinc reagents [(MeCN)₂­Zn­((CF₂)_<i>n</i>)₂­Zn­(MeCN)₂] (<i>n</i> = 3, 4, and 6) is reported. We show that the C4 reagent can readily transmetalate nickel to form a mononuclear perfluoronickelacycle. We also demonstrate that the reagents can be used to prepare novel fluoroorganics containing either perfluoroalkyl ring systems or perfluoroalkyl linked arenes under relatively mild conditions