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Advances in transition metal (Pd, Ni, Fe)-catalyzed cross-coupling reactions using alkyl-organometallics as reaction partners.

3.1. C-M and X-H as Nucleophiles 1806 3.2. C-H and X-M as Nucleophiles 1809 3.2.1. C-Halogen Bond Formations 1809 3.2.2. C-O Bond Formations 1812 3.3. C-H and X-H as Nucleophiles 1812 3.3.1. C-O Bond Formations 1812 3.3.2. C-N Bond Formations 1815 4. Oxidative X-X Bond Formations between Two Nucleophiles 1819 5. Conclusions 1819 Author Information 1819 Biographies 1819 Acknowledgment 1820 References 1820

Bond Formations between Two Nucleophiles: Transition Metal Catalyzed Oxidative Cross-Coupling Reactions

Over the last decade, substantial research has led to the introduction of an impressive number of efficient procedures which allow the selective construction of CC bonds by directly connecting two different CH bonds under oxidative conditions. Common to these methodologies is the generation of the reactive intermediates in situ by activation of both CH bonds. This strategy was introduced by the group of Li as cross-dehydrogenative coupling (CDC) and discloses waste-minimized synthetic alternatives to classic coupling procedures which rely on the use of prefunctionalized starting materials. This Review highlights the recent progress in the field of cross-dehydrogenative C sp 3C formations and provides a comprehensive overview on existing procedures and employed methodologies.

The Cross-Dehydrogenative Coupling of C sp 3H Bonds: A Versatile Strategy for CC Bond Formations

Palladium-catalyzed C-C and C-N bond-forming reactions are among the most versatile and powerful synthetic methods. For the last 15 years, N-heterocyclic carbenes (NHCs) have enjoyed increasing popularity as ligands in Pd-mediated cross-coupling and related transformations because of their superior performance compared to the more traditional tertiary phosphanes. The strong sigma-electron-donating ability of NHCs renders oxidative insertion even in challenging substrates facile, while their steric bulk and particular topology is responsible for fast reductive elimination. The strong Pd-NHC bonds contribute to the high stability of the active species, even at low ligand/Pd ratios and high temperatures. With a number of commercially available, stable, user-friendly, and powerful NHC-Pd precatalysts, the goal of a universal cross-coupling catalyst is within reach. This Review discusses the basics of Pd-NHC chemistry to understand the peculiarities of these catalysts and then gives a critical discussion on their application in C-C and C-N cross-coupling as well as carbopalladation reactions.

Palladium Complexes of N-Heterocyclic Carbenes as Catalysts for Cross-Coupling Reactions—A Synthetic Chemist's Perspective

C–H activation has surfaced as an increasingly powerful tool for molecular sciences, with notable applications to material sciences, crop protection, drug discovery, and pharmaceutical industries, among others. Despite major advances, the vast majority of these C–H functionalizations required precious 4d or 5d transition metal catalysts. Given the cost-effective and sustainable nature of earth-abundant first row transition metals, the development of less toxic, inexpensive 3d metal catalysts for C–H activation has gained considerable recent momentum as a significantly more environmentally-benign and economically-attractive alternative. Herein, we provide a comprehensive overview on first row transition metal catalysts for C–H activation until summer 2018.

3d Transition Metals for C-H Activation.

Copper salts, which are abundant, relatively inexpensive and possess low toxicity, have long been used as versatile catalysts for various reactions in organic synthesis. Recently, the development of Cu-catalyzed or -mediated CH functionalization reactions has gained significant attention. Since the pioneering work of Daugulis on the introduction of 8-aminoquinoline and picolinic acid auxiliaries as removable directing groups in transition metal-catalyzed CH bond activations, the combination of copper salts with these bidentate directing groups has emerged as an innovative strategy for the construction of carbon-carbon or carbon-heteroatom bonds through CH bond cleavage. In addition to the 8-aminoquinoline and picolinamide systems, several other bidentate directing groups including the 2-aminophenyloxazoline group by Yu and Dai and the PIP system by Shi, have been developed as well. This review intends to cover most of the recent advances on copper-catalyzed or -mediated direct sp2 and sp3 CH bond functionalizations assisted by these bidentate directing groups. The major achievements in this area are discussed and catalogued by the type of bonds formed (CC, CO, CN, CS, CP etc.). Special attention is paid to the reaction mechanisms. Selected examples of substrates are listed as well. In addition, a personal outlook is given at the end.

Copper-Catalyzed or -Mediated CH Bond Functionalizations Assisted by Bidentate Directing Groups

Pd-catalyzed decarboxylative arylation of thiazole, benzoxazole, and polyfluorobenzene with substituted benzoic acids.

An efficient copper-catalyzed oxidative Mannich reaction between tertiary amines and methyl ketones

Pd-catalyzed decarboxylative ortho-acylation of O-methyl oximes with phenylglyoxylic acids

Synthesis of Oxindoles through Silver‐Catalyzed Trifluoromethylation–, Difluoromethylation– and Arylsulfonylation–Cyclization Reaction of N‐Arylacrylamides

Ze Tan

Papers

Copper-Catalyzed or -Mediated CH Bond Functionalizations Assisted by Bidentate Directing Groups

Pd-catalyzed decarboxylative arylation of thiazole, benzoxazole, and polyfluorobenzene with substituted benzoic acids.

An efficient copper-catalyzed oxidative Mannich reaction between tertiary amines and methyl ketones

Pd-catalyzed decarboxylative ortho-acylation of O-methyl oximes with phenylglyoxylic acids

Synthesis of Oxindoles through Silver‐Catalyzed Trifluoromethylation–, Difluoromethylation– and Arylsulfonylation–Cyclization Reaction of N‐Arylacrylamides