There is, I think, something ethereal about i —the square root of minus one. I remember first hearing about it at school. It seemed an odd beast at that time—an intruder hovering on the edge of reality.

Usually familiarity dulls this sense of the bizarre, but in the case of i it was the reverse: over the years the sense of its surreal nature intensified. It seemed that it was impossible to write mathematics that described the real world in …

I and i

Catalytic dehydrogenative cross-coupling: forming carbon-carbon bonds by oxidizing two carbon-hydrogen bonds

The site-selective formation of carbon-carbon bonds through direct functionalizations of otherwise unreactive carbon-hydrogen bonds constitutes an economically attractive strategy for an overall streamlining of sustainable syntheses. In recent decades, intensive research efforts have led to the development of various reaction conditions for challenging C-H bond functionalizations, among which transition-metal-catalyzed transformations arguably constitute thus far the most valuable tool. For instance, the use of inter alia palladium, ruthenium, rhodium, copper, or iron complexes set the stage for chemo-, site-, diastereo-, and/or enantioselective C-H bond functionalizations. Key to success was generally a detailed mechanistic understanding of the elementary C-H bond metalation step, which depending on the nature of the metal fragment can proceed via several distinct reaction pathways. Traditionally, three different modes of action were primarily considered for CH bond metalations, namely, (i) oxidative addition with electronrich late transition metals, (ii) σ-bond metathesis with early transition metals, and (iii) electrophilic activation with electrondeficient late transition metals (Scheme 1). However, more recent mechanistic studies indicated the existence of a continuum of electrophilic, ambiphilic, and nucleophilic interactions. Within this continuum, detailed experimental and computational analysis provided strong evidence for novel C-H bond metalationmechanisms relying on the assistance of a bifunctional ligand bearing an additional Lewis-basic heteroatom, such as that found in (heteroatom-substituted) secondary phosphine oxides or most prominently carboxylates (Scheme 1, iv). This novel insight into the nature of stoichiometric metalations has served as stimulus for the development of novel transformations based on cocatalytic amounts of carboxylates, which significantly broadened the scope of C-H bond functionalizations in recent years, with most remarkable progress being made in palladiumor ruthenium-catalyzed direct arylations and direct alkylations. These carboxylate-assisted C-H bond transformations were mostly proposed to proceed via a mechanism in which metalation takes place via a concerted base-assisted deprotonation. To mechanistically differentiate these intramolecular metalations new acronyms have recently been introduced into the literature, such as CMD (concerted metalationdeprotonation), IES (internal electrophilic substitution), or AMLA (ambiphilic metal ligand activation), which describe related mechanisms and will be used below where appropriate. This review summarizes the development and scope of carboxylates as cocatalysts in transition-metal-catalyzed C-H functionalizations until autumn 2010. Moreover, experimental and computational studies on stoichiometric metalation reactions being of relevance to the mechanism of these catalytic processes are discussed as well. Mechanistically related C-H bond cleavage reactions with ruthenium or iridium complexes bearing monodentate ligands are, however, only covered with respect to their working mode, and transformations with stoichiometric amounts of simple acetate bases are solely included when their mechanism was suggested to proceed by acetate-assisted metalation.

Carboxylate-assisted transition-metal-catalyzed C-H bond functionalizations: mechanism and scope.

3.7. Palladium Nanoparticles as Catalysts 888 3.8. Other Transition-Metal Complexes 888 3.9. Transition-Metal-Free Reactions 889 4. Applications 889 4.1. Alkynylation of Arenes 889 4.2. Alkynylation of Heterocycles 891 4.3. Synthesis of Enynes and Enediynes 894 4.4. Synthesis of Ynones 896 4.5. Synthesis of Carbocyclic Systems 897 4.6. Synthesis of Heterocyclic Systems 898 4.7. Synthesis of Natural Products 903 4.8. Synthesis of Electronic and Electrooptical Molecules 906

https://www.chem.ccu.edu.tw/~joyce/referance/ericyang/Chem.%20Rev/Chem.%20Rev.%202007,%20107,%20874-922.pdf

The Sonogashira Reaction: A Booming Methodology in Synthetic Organic Chemistry†

The direct functionalization of C-H bonds in organic compounds has recently emerged as a powerful and ideal method for the formation of carbon-carbon and carbon-heteroatom bonds. This Review provides an overview of C-H bond functionalization strategies for the rapid synthesis of biologically active compounds such as natural products and pharmaceutical targets.

C-H bond functionalization: emerging synthetic tools for natural products and pharmaceuticals

The area of transition-metal-catalyzed direct arylation through cleavage of CH bonds has undergone rapid development in recent years, and is becoming an increasingly viable alternative to traditional cross-coupling reactions with organometallic reagents In particular, palladium and ruthenium catalysts have been described that enable the direct arylation of (hetero)arenes with challenging coupling partners—including electrophilic aryl chlorides and tosylates as well as simple arenes in cross-dehydrogenative arylations Furthermore, less expensive copper, iron, and nickel complexes were recently shown to be effective for economically attractive direct arylations

Transition-metal-catalyzed direct arylation of (hetero)arenes by C-H bond cleavage.

Das Gebiet der ubergangsmetallkatalysierten direkten Arylierung unter C-H-Bindungsbruch hat in den letzten Jahren eine rasante Entwicklung erfahren, was dazu fuhrte, dass sich solche Methoden immer mehr als Alternativen zu den herkommlichen Kreuzkupplungen mit metallorganischen Reagentien etabliert haben Insbesondere wurden zahlreiche Palladium- und Rutheniumkatalysatoren beschrieben, welche die direkte Arylierung von (Hetero)arenen mit anspruchsvollen Reaktionspartnern ermoglichen; hierzu gehoren elektrophile Arylchloride und -tosylate oder auch einfache Arene in gekreuzten dehydrierenden Arylierungen

Übergangsmetallkatalysierte direkte Arylierungen von (Hetero)Arenen durch C-H-Bindungsbruch

Much success has been achieved with platinum-based chemotherapeutic agents, i.e. through interactions with DNA. The long-term application of Pt complexes is thwarted by issues, leading scientists to examine other metals such as palladium which could exhibit complementary modes of action (given emphasis wherever known). Over the last 10 years several research groups have focused on the application of an eclectic array of palladium complexes (of the type PdX2L2, palladacycles and related structures) as potential anti-cancer agents. This review therefore provides readers with an up to date account of the advances that have taken place over the past several decades.

Anti-cancer palladium complexes: a focus on PdX2L2, palladacycles and related complexes.

The late-stage modification of structurally complex peptides bears great potential for drug discovery, crop protection, and the pharmaceutical industry, among others. Whereas traditional approaches largely rely on prefunctionalizations, C-H activation catalysis has in recent years emerged as an increasingly powerful tool for post-translational peptide modifications in a step-economic manner. Herein, we summarize recent progress in organometallic C-H activation on peptides until June 2018, including position- and chemoselective palladium-, ruthenium-, and manganese-catalyzed processes.

Anant R. Kapdi

Papers

Transition-metal-catalyzed direct arylation of (hetero)arenes by C-H bond cleavage.

Übergangsmetallkatalysierte direkte Arylierungen von (Hetero)Arenen durch C-H-Bindungsbruch

Anti-cancer palladium complexes: a focus on PdX2L2, palladacycles and related complexes.

Late-Stage Peptide Diversification by Position-Selective C-H Activation.

Simple Palladium(II) Precatalyst for Suzuki−Miyaura Couplings: Efficient Reactions of Benzylic, Aryl, Heteroaryl, and Vinyl Coupling Partners