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Regioselective Direct C-H Alkylation of NH Indoles and Pyrroles by a Palladium/Norbornene-Cocatalyzed Process

Nitrogen-containing heterocycles, including 1H-indoles and electron-deficient 1H-pyrroles, undergo a palladium/norbornene-cocatalyzed regioselective alkylation at the C–H bond adjacent to the NH group. A primary alkyl halide is used as the …

Vinylcyclopropane Derivatives in Transition-Metal-Catalyzed Cycloadditions for the Synthesis of Carbocyclic Compounds.

Vinylcyclopropane (VCP) derivatives participate in a variety of transition-metal-catalyzed multicomponent cycloadditions to produce five- to eight-membered carbocycles. Various cycloaddition modes provide novel approaches to mono-, bi-, and …

Palladium-Catalyzed Direct C-H Alkylation of Electron-Deficient Pyrrole Derivatives

**The apparent and the real:** What looks like a Friedel–Crafts alkylation reaction of electron-deficient pyrroles is actually a PdII-catalyzed, norbornene-mediated CH activation reaction, in which the alkylation of the pyrrole core occurs by …

Pd(II)-Catalyzed Regioselective 2-Alkylation of Indoles via a Norbornene-Mediated C–H Activation: Mechanism and Applications.

A palladium-catalyzed direct 2-alkylation reaction of free N-H indoles was developed based on a norbornene-mediated regioselective cascade C–H activation. The detailed reaction mechanism was investigated by NMR spectroscopic analyses, …

Palladium-Catalyzed Direct 2-Alkylation of Indoles by Norbornene-Mediated Regioselective Cascade C–H Activation

A palladium-catalyzed direct 2-alkylation reaction of free N-H indoles has been developed. This reaction relies on a norbornene-mediated cascade C–H activation process at the indole ring, which features high regioselectivity and excellent functional …

Density Functional Theory Study of the Mechanisms and Stereochemistry of the Rh(I)-Catalyzed Intramolecular [3+2] Cycloadditions of 1-Ene- and 1-Yne-Vinylcyclopropanes.

The mechanisms, structures of all stationary points involved, and kinetic and thermodynamic parameters of the Rh(I)-catalyzed intramolecular [3+2] cycloaddition reactions of 1-ene- and 1-yne-vinylcyclopropanes (1-ene-VCPs and 1-yne-VCPs) have been …

Rh(I)-Catalyzed [(3 + 2) + 1] Cycloaddition of 1-Yne/Ene-vinylcyclopropanes and CO: Homologous Pauson−Khand Reaction and Total Synthesis of (±)-α-Agarofuran.

A novel Rh(I)-catalyzed [(3 + 2) + 1] cycloaddition, which can be regarded as a homologous Pauson−Khand reaction, was developed to synthesize bicyclic cyclohexenones and cyclohexanones, enabling a new approach for synthesis of six-membered …

Rh(I)-Catalyzed Intramolecular [3 + 2] Cycloaddition Reactions of 1-Ene-, 1-Yne- and 1-Allene-Vinylcyclopropanes.

New Rh(I)-catalyzed intramolecular [3 + 2] cycloaddition reactions of 1-ene-, 1-yne and 1-allene-vinylcyclopropanes have been developed, affording an efficient and versatile synthesis of cyclopentane- and cyclopentene-embedded bicyclic structures.

New Insights into the Torquoselectivity of the Staudinger Reaction.

To understand the torquoselectivity and the electronic effects of the Staudinger reaction, a study using a combination of experiments and DFT calculations has been conducted for the reactions of an unsymmetric cyclic ketene and cyclic imines with …

Rh(I)-Catalyzed Intramolecular [3 + 2] Cycloaddition of trans-Vinylcyclopropane-enes.

Vinylcyclopropane (VCP) has been well applied as a five-carbon component, rather than a three-carbon component, in transition-metal catalyzed cycloadditions. Here we demonstrate a Rh(I)-catalyzed [3 + 2] reaction of trans-VCP-enes, where VCP acts as …