Nickel-Catalyzed Deaminative Acylation of Activated Aliphatic Amines with Aromatic Amides via C-N Bond Activation.

Deaminative functionalization of aliphatic primary amines has great synthetic utility. Herein, we describe a Ni-catalyzed reductive deaminative cross-electrophile coupling reaction between Katritzky salts and aromatic amides. This work provides examples of the synthesis of various ketones from alkylpyridinium salts, including both primary and secondary alkylamines. Given its mild reaction conditions and high functional group tolerance, this cross-coupling strategy is expected to be useful for late-stage functionalization of complex compounds.

Reduced Knoevenagel Reaction of Acetetracenylene-1,2-dione with Acceptor Units for Luminescent Tetracene Derivatives.

Acetetracenylene-1,2-dione reacted with 3-ethylrhodanine in the presence of piperidine and Hantzsch ester via a Knoevenagel condensation-reduction sequence to give a tetracene-rhodanine adduct. This reduced Knoevenagel product exhibited magenta luminescence with a fluorescence quantum yield of φ = 0.34 and fluorescence lifetime of τ = 13.2 ns in toluene. Electrochemical studies and charge carrier transport measurements revealed ambipolar properties with hole and electron mobilities of 5.1 × 10-7 and 1.6 × 10-4 cm2/(V s), respectively.

Rhodium(III)-Catalyzed Directed C-H Coupling with Methyl Trifluoroacrylate: Diverse Synthesis of Fluoroalkenes and Heterocycles.

An example of Rh-catalyzed C-H activation with methyl trifluoroacrylate for the synthesis of fluoroolefins and heterocycles (benzoindolizines) is reported. The types of products were determined by the directing group. The benzoindolizines and fluoroolefins were obtained by using pyridine and pyrazole as the directing group, correspondingly. These transformations present a number of advantages, such as oxidant-free reaction conditions and broad functional group tolerance. Moreover, this reaction greatly extends the application of fluoroolefins.

Ligand-Controlled Regiodivergent Copper-Catalyzed Alkylboration of Alkenes.

A novel copper-catalyzed regiodivergent alkylboration of alkenes with bis(pinacolato)diboron and alkyl halides has been developed. The regioselectivity of the alkylboration was controlled by subtle differences in the ligand structure. The reaction thus enables the practical, regiodivergent synthesis of two different alkyl boronic esters with complex structures from a single alkene.

Pd-Catalyzed Regioselective Activation of gem-Difluorinated Cyclopropanes: A Highly Efficient Approach to 2-Fluorinated Allylic Scaffolds.

An unprecedented Pd-catalyzed regioselective activation of gem-difluorinated cyclopropanes induced by C-C bond cleavage is reported. It provides a general and efficient access to a variety of 2-fluoroallylic amines, ethers, esters, and alkylation products in high Z-selectivity, which are important skeletons in many biologically active molecules. In addition, the transformation represents the first general application of gem-difluorinated cyclopropanes as reaction partners in transition-metal-catalyzed cross-coupling reaction.