Organofluorine compounds are widely used in all aspects of the chemical industry. Although tetrafluoroethylene (TFE) is an example of an economical bulk organofluorine feedstock, the use of TFE is mostly limited to the production of poly(tetrafluoroethylene) and copolymers with other alkenes. Furthermore, no catalytic transformation of TFE that involves carbon-fluorine bond activation has been reported to date. We herein report the first example of a palladium-catalyzed coupling reaction of TFE with arylzinc reagents in the presence of lithium iodide, giving α,β,β-trifluorostyrene derivatives in excellent yields.

A catalyst system derived from nickel and cocatalytic AlMe2Cl effects the intramolecular arylcyanation of alkenes. The reaction takes place in an exclusive exo-dig manner to give a wide range of nitriles having a benzylic quaternary carbon in good yields. Detailed investigations are described on the scope and mechanism as well as preliminary results on the asymmetric version of the reaction to provide novel access to chiral quaternary stereocenters.

The reversible oxidative cyclization of dienes and aldehydes with nickel(0) proceeded to give eta(3):eta(1)-allylalkoxynickel complexes. The treatment of these complexes with carbon monoxide led to the formation of the corresponding lactone and/or the regeneration of a butadiene and an aldehyde concomitant with the formation of Ni(CO)(3)(PCy(3)). The scission of the nickel-oxygen bond of the allylalkoxy complexes with ZnMe(2) leading to eta(3)-allyl(methyl)nickel was very efficient to suppress the reverse reaction of the oxidative cyclization. The methylated eta(3)-allylnickel compound underwent the reductive elimination. The carbonylative coupling reaction of the eta(3)-allyl(methyl)nickel proceeded as well under a carbon monoxide atmosphere. Similarly, the addition of Me(3)SiCl to eta(3):eta(1)-allylalkoxynickel complexes was also efficient for the inhibition of the reverse reaction. The resulting eta(3)-1-siloxyethylallylnickel complex was treated with carbon monoxides followed by the addition of MeOH to give the expected hydroxyester. This method is efficient as well even for the eta(3):eta(1)-allyl(alkoxy)nickel complex containing acetone as a component, which was so prone to undergo the reverse reaction hampering its isolation. The isolation of the eta(3):eta(1)-allylalkoxynickel complex containing ketone as a component was made easier by the use of heavier butadiene and ketone, such as 2,3-dibenzyl-1,3-butadiene and benzophenone or by the use of cyclobutanone. The reaction with styrene oxide gave the eta(3):eta(1)-allylalkoxynickel containing phenylacetoaldehyde, an isomer of styrene oxide.

Cyclopropyl phenyl ketone underwent oxidative addition to Ni(PCy3) generated from Ni(cod)2 and PCy3 to give a nickeladihydropyran, which is a key intermediate for the Ni(0)-catalyzed homo- or heterocycloaddition to give cyclopentane compounds having two carbonyl substituents at the 1,3-position.

The formation of a nickeladihydrofuran by oxidative cyclization of an alkyne and an aldehyde with nickel(0) has been demonstrated; the transformation of the nickeladihydrofuran into an enone by decomposition, a lactone by carbonylation and an allylic alcohol by treatment with ZnMe(2) suggests that nickeladihydrofuran is an important key intermediate in a variety of catalytic reactions.

Direct oxidative cyclization of (eta2:eta2-CH2=CHCH2C6H4CHO)Ni(PR3) to form the nickelacycle and drastic acceleration of the cyclization by the addition of Me3SiOTf were observed. (eta2-PhCHO)Ni(PCy3)2 also reacted with Me3SiOTf to give (eta1:eta1-Me3SiOCH(Ph))Ni(PCy3)OTf.

Given the growing demand for green and sustainable chemical processes, the catalytic reductive alkylation of amines with main-group catalysts of low toxicity and molecular hydrogen as the reductant would be an ideal method to functionalize amines. However, such a process remains challenging. Herein, a novel reductive alkylation system using H is presented, which proceeds via a tandem reaction that involves the B(2,6-ClCH)( p-HCF)-catalyzed formation of an imine and the subsequent hydrogenation of this imine catalyzed by a frustrated Lewis pair (FLP). This reductive alkylation reaction generates HO as the sole byproduct and directly functionalizes amines that bear a remarkably wide range of substituents including carboxyl, hydroxyl, additional amino, primary amide, and primary sulfonamide groups. The synthesis of isoindolinones and aminophthalic anhydrides has also been achieved by a one-pot process that consists of a combination of the present reductive alkylation with an intramolecular amidation and intramolecular dehydration reactions, respectively. The reaction showed a zeroth-order and a first-order dependence on the concentration of an imine intermediate and B(2,6-ClCH)( p-HCF), respectively. In addition, the reaction progress was significantly affected by the concentration of H. These results suggest a possible mechanism in which the heterolysis of H is facilitated by the FLP comprising THF and B(2,6-ClCH)( p-HCF).

Ni(cod)(2)/P(t)Bu(3) system catalyzed the dimerization of terminal alkynes to give (E)-head-to-head dimerization products, in which the stannylacetylene dimer could be applied to a one-pot synthesis of a conjugated enyne, when combined with Migita-Stille coupling.