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

Once considered the 'holy grail' of organometallic chemistry, synthetically useful reactions employing C-H bond activation have increasingly been developed and applied to natural product and drug synthesis over the past decade. The ubiquity and relative low cost of hydrocarbons makes C-H bond functionalization an attractive alternative to classical C-C bond forming reactions such as cross-coupling, which require organohalides and organometallic reagents. In addition to providing an atom economical alternative to standard cross - coupling strategies, C-H bond functionalization also reduces the production of toxic by-products, thereby contributing to the growing field of reactions with decreased environmental impact. In the area of C-C bond forming reactions that proceed via a C-H activation mechanism, rhodium catalysts stand out for their functional group tolerance and wide range of synthetic utility. Over the course of the last decade, many Rh-catalyzed methods for heteroatom-directed C-H bond functionalization have been reported and will be the focus of this review. Material appearing in the literature prior to 2001 has been reviewed previously and will only be introduced as background when necessary. The synthesis of complex molecules from relatively simple precursors has long been a goal for many organic chemists. The ability to selectively functionalize a molecule with minimal pre-activation can streamline syntheses and expand the opportunities to explore the utility of complex molecules in areas ranging from the pharmaceutical industry to materials science. Indeed, the issue of selectivity is paramount in the development of all C-H bond functionalization methods. Several groups have developed elegant approaches towards achieving selectivity in molecules that possess many sterically and electronically similar C-H bonds. Many of these approaches are discussed in detail in the accompanying articles in this special issue of Chemical Reviews. One approach that has seen widespread success involves the use of a proximal heteroatom that serves as a directing group for the selective functionalization of a specific C-H bond. In a survey of examples of heteroatom-directed Rh catalysis, two mechanistically distinct reaction pathways are revealed. In one case, the heteroatom acts as a chelator to bind the Rh catalyst, facilitating reactivity at a proximal site. In this case, the formation of a five-membered metallacycle provides a favorable driving force in inducing reactivity at the desired location. In the other case, the heteroatom initially coordinates the Rh catalyst and then acts to stabilize the formation of a metal-carbon bond at a proximal site. A true test of the utility of a synthetic method is in its application to the synthesis of natural products or complex molecules. Several groups have demonstrated the applicability of C-H bond functionalization reactions towards complex molecule synthesis. Target-oriented synthesis provides a platform to test the effectiveness of a method in unique chemical and steric environments. In this respect, Rh-catalyzed methods for C-H bond functionalization stand out, with several syntheses being described in the literature that utilize C-H bond functionalization in a key step. These syntheses are highlighted following the discussion of the method they employ.

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Rhodium-Catalyzed C-C Bond Formation via Heteroatom-Directed C-H Bond Activation

N-Heterocyclic Carbenes in Late Transition Metal Catalysis

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.

Ruthenium(II)-Catalyzed C–H Bond Activation and Functionalization

Palladium-Catalyzed C-S Bond Cleavage With Allenoates: Synthesis of Tetrasubstituted 2-Alkenylfuran Derivatives

Organic Syntheses via Transition Metal Complexes. 96.1 1-Azacycloalkene and 2-Azabicycloalkene Derivatives of 4-Amino-1-metalla-1,3-dienes by Reaction of Saturated Lactims with (1-Alkynyl)carbene Complexes of Chromium and Tungsten

N-Arylamides were exclusively obtained in moderate to good yields from selenium-catalyzed reactions of nitroaromatics with amides in the presence of CO and mixed organic bases Et3N and DBU.

N‐Arylamides from Selenium‐Catalyzed Reactions of Nitroaromatics and Amides in the Presence of Carbon Monoxide and Mixed Organic Bases

Four types of N-heterocyclic ring systems were successfully constructed from the reactions of 1-alkynyl Fischer carbene complexes (OC)5MC(OEt)C⋮CPh (1) (M = Cr, W) and substituted pyrazolinones (2). Reactions of 1 with 3-methyl-2-pyrazolin-5-one (2a), 3-n-propyl-2-pyrazolin-5-one (2b), 3,4-dimethyl-2-pyrazolin-5-one (2c), 3,4-trimethylene-2-pyrazolin-5-one (2d), or 3,4-tetramethylene-2-pyrazolin-5-one (2e) generated three kinds of Fischer aminocarbene complexes (3−5), and reactions of 1 with phenyl-substituted pyrazolinones, i.e., 3-phenyl-2-pyrazolin-5-one (2f) and its tautomer 3-phenyl-3-pyrazolin-5-one (2g), gave Fischer alkoxycarbene complexes (6) as the major products and aminocarbene complexes of types 3−5 as the minor products. Multiple tautomerism of pyrazolinones is attributed to the versatile formation of N-heterocyclic Fischer carbene complexes. Oxidative demetalation of complexes 3−6 with pyridine N-oxide or m-chloroperoxybenzoic acid efficiently afforded organic carbonyl products, and thus, s...

Tautomerism-Dependent Ring Construction of N-Heterocyclic Compounds from the Reactions of 1-Alkynyl Fischer Carbene Complexes and Substituted Pyrazolinones

The invention relates to methods of making monodisperse nanocrystals comprising the steps of reducing a copper salt with a reducing agent, providing a passivating agent comprising a nitrogen and/or an oxygen donating moitey and isolating the copper nanocrystals. Moreover, the invention relates to methods for making a copper film comprising the steps of applying a solvent comprising copper nanocrystals onto a substrate and heating the substrate to form a film of continuous bulk copper from said nanocrystals. Finally, the invention also relates to methods for filling a feature on a substrate with copper comprising the steps of applying a solvent comprising copper nanocrystals onto the featured substrate and heating the substrate to fill the feature by forming continuous bulk copper in the feature.

Zhengkun Yu

Papers

Palladium-Catalyzed C-S Bond Cleavage With Allenoates: Synthesis of Tetrasubstituted 2-Alkenylfuran Derivatives

Organic Syntheses via Transition Metal Complexes. 96.1 1-Azacycloalkene and 2-Azabicycloalkene Derivatives of 4-Amino-1-metalla-1,3-dienes by Reaction of Saturated Lactims with (1-Alkynyl)carbene Complexes of Chromium and Tungsten

N‐Arylamides from Selenium‐Catalyzed Reactions of Nitroaromatics and Amides in the Presence of Carbon Monoxide and Mixed Organic Bases

Tautomerism-Dependent Ring Construction of N-Heterocyclic Compounds from the Reactions of 1-Alkynyl Fischer Carbene Complexes and Substituted Pyrazolinones

Methods of filling a feature on a substrate with copper nanocrystals