Palladium-Catalyzed, <i>ortho</i>-Selective C–H Halogenation of Benzyl Nitriles, Aryl Weinreb Amides, and Anilides

A palladium-catalyzed, <i>ortho</i>-selective C–H halogenation methodology is reported herein. The highlight of the work is the highly selective C­(sp²)–H functionalization of benzyl nitriles in the presence of activated C­(sp³)–H bond, which results in good yields of the halogenated products with excellent regioselectivity. Along with benzyl nitriles, aryl Weinreb amides and anilides have been evaluated for the transformation using aprotic conditions. Mechanistic studies yield interesting aspects with respect to the pathway of the reaction and the directing group abilities

Ruthenium-Catalyzed, Site-Selective C–H Allylation of Indoles with Allyl Alcohols as Coupling Partners

A new ruthenium-catalyzed, heteroatom-directed strategy for C–H allylation of indoles is described. The use of allyl alcohols as coupling partners as well as pyridine as the removable directing group is highlighted. This methodology provides access to C2-allylated indoles by utilizing a strategy that does not require prefunctionalization of either of the coupling partners

Catalyst-Controlled Chemodivergent Reactivity of Vinyl Cyclopropanes: A Selective Approach toward Indoles and Aniline Derivatives

Herein, we disclose a catalyst-controlled chemodivergent approach to access C2-substituted indoles and diverse aniline derivatives with good chemo- and stereoselectivity by employing vinylcyclopropanes (VCPs) as coupling partners via a tandem C–H/C–C activation/annulation strategy. The key feature of this work is the divergent reactivity profile showcased by VCPs, going beyond allylation under a high-valent Rh-/MPAA catalyst system

Ruthenium-Catalyzed Heteroatom-Directed Regioselective C–H Arylation of Indoles Using a Removable Tether

A new approach to C-2 arylated indoles has been developed by utilizing a ruthenium-catalyzed, heteroatom-directed regioselective C–H arylation. The reaction is highly site-selective and results in very good yields. The highlight of the work is the use of a removable directing group and compatibility of the catalytic system with halogen functional groups in the substrates

Catalyst-Controlled Chemodivergent Reactivity of Vinyl Cyclopropanes: A Selective Approach toward Indoles and Aniline Derivatives

Herein, we disclose a catalyst-controlled chemodivergent approach to access C2-substituted indoles and diverse aniline derivatives with good chemo- and stereoselectivity by employing vinylcyclopropanes (VCPs) as coupling partners via a tandem C–H/C–C activation/annulation strategy. The key feature of this work is the divergent reactivity profile showcased by VCPs, going beyond allylation under a high-valent Rh-/MPAA catalyst system

Ruthenium-Catalyzed Heteroatom-Directed Regioselective C–H Arylation of Indoles Using a Removable Tether

A new approach to C-2 arylated indoles has been developed by utilizing a ruthenium-catalyzed, heteroatom-directed regioselective C–H arylation. The reaction is highly site-selective and results in very good yields. The highlight of the work is the use of a removable directing group and compatibility of the catalytic system with halogen functional groups in the substrates

Ruthenium-Catalyzed Heteroatom-Directed Regioselective C–H Arylation of Indoles Using a Removable Tether

A new approach to C-2 arylated indoles has been developed by utilizing a ruthenium-catalyzed, heteroatom-directed regioselective C–H arylation. The reaction is highly site-selective and results in very good yields. The highlight of the work is the use of a removable directing group and compatibility of the catalytic system with halogen functional groups in the substrates

One Substrate, Two Modes of C–H Functionalization: A Metal-Controlled Site-Selectivity Switch in C–H Arylation Reactions

A unique site-selectivity switch has been achieved in the ruthenium-catalyzed C–H arylation reaction of <i>N</i>-acetyl-1,2-dihydroisoquinolines. This metal-mediated switch is antipodal to the previous report on the palladium-mediated C-4 C–H arylation on the same substrate. Mechanistic details reveal interesting aspects of the reaction pathway, and kinetic studies bring out the difference in the modes of C–H activation adopted by the two catalytic systems

Palladium(II)-Catalyzed, Heteroatom-Directed, Regioselective C–H Nitration of Anilines Using Pyrimidine as a Removable Directing Group

A new palladium-catalyzed, heteroatom-directed strategy for C–H nitration of anilines is described. This C–H functionalization reaction is highly <i>ortho</i>-selective and results in very good yields. The highlight of the work is the use of pyrimidine as the removable directing group. This approach constitutes one of the rare methods of <i>ortho</i>-nitration of anilines, a reaction that is normally very difficult to achieve via traditional approaches