Juhyeon Park

Comparative Catalytic Activity of Group 9 [Cp*MIII] Complexes: Cobalt‐Catalyzed CH Amidation of Arenes with Dioxazolones as Amidating Reagents

A procedure for the [Cp*Co(III)]-catalyzed direct C-H amidation of arenes with dioxazolone has been developed. This reaction proceeds under straightforward and mild conditions with a broad range of substrates, including anilides. A comparative study on the catalytic activity of Group 9 [{Cp*MCl2}2] complexes revealed the unique efficiency of the cobalt catalyst.

Synthesis of Phosphoramidates: A Facile Approach Based on the C–N Bond Formation via Ir-Catalyzed Direct C–H Amidation

A new synthetic route to phosphoramidates by intermolecular C-H amidation is presented. Substrates with assorted directing groups were activated by an iridium-based catalyst system and reacted with a number of phosphoryl azides, executing efficient phosphoramidate synthesis via C-N bond formations.

A Direct Access to 7-Aminoindoles via Iridium-Catalyzed Mild C–H Amidation of N-Pivaloylindoles with Organic Azides

Ir(III)-catalyzed regioselective direct C-7 amidation of indoles in reaction with organic azides has been developed. While its efficiency was varied by the choice of N-directing groups, N-pivaloylindoles were most effective in undergoing the desired amidation at room temperature over a broad range of substrates. The reaction was scalable, and deprotection of the chelation group was also facile.

Chemoselective Silylative Reduction of Conjugated Nitriles under Metal‐Free Catalytic Conditions: β‐Silyl Amines and Enamines

The B(C6F5)3-catalyzed silylative reduction of conjugated nitriles has been developed to afford synthetically valuable β-silyl amines. The reaction is chemoselective and proceeds under mild conditions. Mechanistic elucidation indicates that it proceeds by rapid double hydrosilylation of the conjugated nitrile to an enamine intermediate which is subsequently reduced to the β-silyl amine, thus forming a new C(sp(3))-Si bond. Based on this mechanistic understanding, a preparative route to enamines was also established using bulky silanes.

Boron-Catalyzed Silylative Reduction of Nitriles in Accessing Primary Amines and Imines

Silylative reduction of nitriles was studied under transition metal-free conditions by using B(C6F5)3 as a catalyst with hydrosilanes as a reductant. Alkyl and (hetero)aryl nitriles were efficiently converted to primary amines or imines under mild conditions. The choice of silanes was found to determine the selectivity: while a full reduction of nitriles was highly facile, the use of sterically bulky silanes allowed for the partial reduction leading to N-silylimines.

Iterative C-H Functionalization Leading to Multiple Amidations of Anilides

Polyaminobenzenes were synthesized by the ruthenium-catalyzed iterative C-H amidation of anilides using dioxazolones as an amino source. This strategy could be implemented by the sequential activation of C-H bonds of formerly generated compounds by cascade chelation assistance of newly installed amide groups. Computational studies provided a rationale.

Comparison of the Reactivities and Selectivities of Group 9 [Cp*MIII] Catalysts in C−H Functionalization Reactions

Pentamethylcyclopentadienyl (Cp*)-based Group 9 metal (Co, Rh, or Ir) catalysts have emerged as powerful tools for C-H functionalization reactions. Whilst a diverse range of organic transformations have been developed by using [Cp*MIII ] catalysts, they have often exhibited orthogonal reactivities and varied selectivities that depended on the choice of the central metal atom. An understanding of the physicochemical properties of the metals, as well as of their reaction mechanisms, has led to significant expansion of the synthetic scope of C-H functionalization reactions. This Focus Review summarizes and discusses the comparative catalytic reactivities and selectivities of the [Cp*MIII ] catalysts, with an emphasis on metal-dependent pathway-switching by considering the mechanistic rationale.