Cu(II)-Catalyzed Aminocyclization of -Propargyl Hydrazones to Substituted Pyrazolines.

An efficient route for the copper(II)-catalyzed synthesis of substituted pyrazolines from readily accessible -propargyl hydrazones has been reported under open flask conditions via intramolecular C-N bond formation. -acyl and -tosyl-substituted pyrazolines have been prepared in moderate to excellent yields. Mechanistic investigations using NMR, high-resolution mass spectrometry (HRMS), and Hammett analyses suggest that the Cu(II) catalyst generally acts as a Lewis acid to form an iminium-ion intermediate via cyclization, which afforded the desired pyrazolines upon hydrolysis.

Hydrodeoxygenative Coupling and Transformation of Aldehydes at a N-Derived Tetranuclear Titanium Imide/Hydride Framework.

Carbon-carbon bond formation via coupling of two organic components is among the most important chemical transformations in organic synthesis. Herein, we report an unprecedented hydrodeoxygenative coupling of aromatic aldehydes to form bibenzyls by a N-derived tetranuclear titanium imide/hydride complex [(Cp'Ti)(μ-NH)(μ-H)] (; Cp' = CMeSiMe). Further reactions with the corresponding aldehydes under air afford hydrobenzamides together with a titanium oxo complex.

B(CF)-catalyzed dehydrogenative cyclization of -tosylhydrazones and anilines a Lewis adduct: a combined experimental and computational investigation.

Tris(pentafluorophenyl)borane-catalyzed dehydrogenative-cyclization of -tosylhydrazones with aromatic amines has been disclosed. This metal-free catalytic protocol is compatible with a range of functional groups to provide both symmetrical and unsymmetrical 3,4,5-triaryl-1,2,4-triazoles. Mechanistic experiments and density functional theory (DFT) studies suggest an initial Lewis adduct formation of -tosylhydrazone with B(CF) followed by sequential intermolecular amination of the borane adduct with aniline, intramolecular cyclization and frustrated Lewis pair (FLP)-catalyzed dehydrogenation for the generation of substituted 1,2,4-triazoles.

Boron-Catalyzed -Alkylation of Arylamines and Arylamides with Benzylic Alcohols.

A sustainable boron-based catalytic approach for chemoselective -alkylation of primary and secondary aromatic amines and amides with primary, secondary, and tertiary benzylic alcohols has been presented. The metal-free protocol operates at low catalyst loading, tolerates several functional groups, and generates HO as the sole byproduct. Preliminary mechanistic studies were performed to demonstrate the crucial role of boron catalyst for the activation of the intermediate dibenzyl ether and to identify the rate-determining step.

Manganese-Catalyzed Divergent Markovnikov Addition and [2+2+2] Cycloaddition of 2-Carbonyl Indanone with Terminal Alkyne.

Herein, we report on manganese-catalyzed regioselective Markovnikov addition and [2+2+2] cycloaddition of 2-carbonyl indanones with terminal alkynes. This method provides an efficient approach for the construction of all-carbon quaternary centers and complex polycyclic hydrocarbon frameworks by the formation of new carbon-carbon single bonds in a regio- and stereoselective manner. Preliminary mechanistic experiments involving deuterium labeling, kinetic, catalytic, and stoichiometric reactions with plausible intermediates were performed to shed light on the reaction mechanism.

Conversion of Dinitrogen to Nitriles at a Multinuclear Titanium Framework.

Activation and functionalization of N2 : A mixed diimide/dinitride tetranuclear titanium complex formed by activation of dinitrogen served as a unique platform for the synthesis of nitriles. Functional groups such as aromatic C-X (X=Cl, Br, I) bonds, nitro groups, and ammonia-sensitive aldehyde and chloromethyl moieties were compatible with the synthetic method.

Copper(II)-catalyzed aerobic oxidative synthesis of substituted 1,2,3- and 1,2,4-triazoles from bisarylhydrazones via C-H functionalization/C-C/N-N/C-N bonds formation.

An unprecedented copper(II)-catalyzed aerobic oxidative synthesis of 2,4,5-triaryl-1,2,3-triazoles and 1,3,5-triaryl-1,2,4-triazoles from bisarylhydrazones as the common starting precursor has been achieved via cascade C-H functionalization/C-C/N-N/C-N bonds formation under mild reaction conditions. One of the enthralling outcomes of this strategy is the copper(II)-catalyzed room temperature C-H functionalization/C-N bond formation in presence of air, which has been accomplished during the synthesis of substituted 1,2,4-triazoles. This new class of compounds could give prospective luminescence as an iconic component in the area of pharmaceutical and biological sciences.

Copper-mediated synthesis of substituted 2-aryl-N-benzylbenzimidazoles and 2-arylbenzoxazoles via C-H functionalization/C-N/C-O bond formation.

An efficient method for the transformation of N-benzyl bisarylhydrazones and bisaryloxime ethers to functionalized 2-aryl-N-benzylbenzimidazoles and 2-arylbenzoxazoles is described. The protocol involves a copper(II)-mediated cascade C-H functionalization/C-N/C-O bond formation under neutral conditions. Substrates having either electron-donating or -withdrawing substituents undergo the cyclization to afford the target heterocycles at moderate temperature.

Copper(II)-catalyzed conversion of bisaryloxime ethers to 2-arylbenzoxazoles via C-H functionalization/C-N/C-O bonds formation.

A copper(II)-catalyzed conversion of bisaryloxime ethers to 2-arylbenzoxazoles has been developed. The reaction involves a cascade C-H functionalization and C-N/C-O bond formation under oxygen atmosphere.