6.4. Polyynes 3123 6.5. Using R-Hydroxy Stannanes 3124 6.6. Using the Hurtley Reaction 3124 6.7. Using a Methylenation Reaction 3125 7. Conclusions and Future Prospects 3125 8. Uncommon Abbreviations 3125 9. Acknowledgments 3125 10. Note Added in Proof 3125 11. References 3126 * Authorstowhomcorrespondenceshouldbeaddressed(evano@chimie.uvsq.fr, nicolas.blanchard@uha.fr). † Université de Versailles Saint Quentin en Yvelines. ‡ Université de Haute-Alsace. Chem. Rev. 2008, 108, 3054–3131 3054

Copper-mediated coupling reactions and their applications in natural products and designed biomolecules synthesis.

Copper-catalyzed Ullmann condensations are key reactions for the formation of carbon-heteroatom and carbon-carbon bonds in organic synthesis. These reactions can lead to structural moieties that are prevalent in building blocks of active molecules in the life sciences and in many material precursors. An increasing number of publications have appeared concerning Ullmann-type intermolecular reactions for the coupling of aryl and vinyl halides with N, O, and C nucleophiles, and this Minireview highlights recent and major developments in this topic since 2004.

Catalytic C-C, C-N, and C-O Ullmann-type coupling reactions.

2.4. Tandem sp-sp Coupling/Cyclization 3418 3. Cycloaddition Reactions 3418 3.1. [3+2] Cycloaddition 3418 3.1.1. Triazole/Isoxazole-Forming Reactions 3418 3.1.2. Reactions of Azomethine Ylides 3419 3.1.3. Cycloaddition of Nitrones 3422 3.1.4. Other [3+2] Reaction 3422 3.2. [4+2] Heterocycloaddition 3422 3.3. [2+2] Cycloaddition 3424 4. Cycloisomerization of Enynes/Diynes 3425 5. Intramolecular Friedel-Crafts-Type Reactions 3428 6. Reactions of R-Diazocarbonyl Compounds 3429 7. Aziridination of Olefins 3431 8. N/O-Vinylation/Arylation 3431 9. Radical Cyclization of Haloalkenes and Haloalkynes 3433

Coinage Metal-Assisted Synthesis of Heterocycles

From 2000 to mid-2010: a fruitful decade for the synthesis of pyrazoles.

Heterocycles constitute the largest and the most diverse family of organic compounds Among them, aromatic heterocycles represent structural motifs found in a great number of biologically active natural and synthetic compounds, drugs, and agrochemicals Moreover, aromatic heterocycles are widely used for synthesis of dyes and polymeric materials of high value 1 There are numerous reports on employment of aromatic heterocycles as intermediates in organic synthesis 2

Although, a variety of highly efficient methodologies for synthesis of aromatic heterocycles and their derivatives have been reported in the past, the development of novel methodologies is in cuntinious demand Particlularly, development of new synthetic approaches toward heterocycles, aiming at achieving greater levels of molecular complexity and better functional group compatibilities in a convergent and atom economical fashions from readily accessible starting materials and under mild reaction conditions, is one of a major research endeavor in modern synthetic organic chemistry Transition metal-catalyzed transformations, which often help to meet the above criteria, are among the most attractive synthetic tools

Several excellent reviews dealing with transition metal-catalyzed synthesis of heterocyclic compounds have been published in literature during recent years Many of them highlighted the use of a particular transition metal, such as gold,3 silver,4 palladium,5 copper,6 cobalt,7 ruthenium,8 iron,9 mercury,10 rare-earth metals,11 and others Another array of reviews described the use of a specific kind of transformation, for instance, intramolecular nucleophilic attack of heteroatom at multiple C–C bonds,12 Sonogashira reaction,13 cycloaddition reactions,14 cycloisomerization reactions,15 C–H bond activation processes,16 metathesis reactions,17 etc Reviews devoted to an application of a particular type of starting materials have also been published Thus, for example, applications of isocyanides,18 diazocompounds,19 or azides20 have been discussed In addition, a significant attention was given to transition metal-catalyzed multicomponent syntheses of heterocycles21 Finally, syntheses of heterocycles featuring formation of intermediates, such as nitrenes,22 vinylidenes,23 carbenes, and carbenoids24 have also been reviewed

The main focus of the present review is a transition metal-catalyzed synthesis of aromatic monocyclic heterocycles The organization of the review is rather classical and is based on a heterocycle, categorized in the following order: (a) ring size of heterocycle, (b) number of heteroatoms, (c) type of heterocycle, and (d) a class of transformation involved A brief mechanistic discussion is given to provide information about a possible reaction pathway when necessary The review mostly discusses recent literature, starting from 200425 until the end of 2011, however, some earlier parent transformations are discussed when needed

Transition Metal-Mediated Synthesis of Monocyclic Aromatic Heterocycles

Domino Cu-Catalyzed CN Coupling/Hydroamidation: A Highly Efficient Synthesis of Nitrogen Heterocycles†

Copper-catalyzed vinylation of hydrazides. A regioselective entry to highly substituted pyrroles.

A modular route to highly substituted pyrroles has been developed. This transformation consists of two sequential copper-catalyzed vinylations of bis-Boc-hydrazine followed by thermal rearrangement/cyclization. A wide variety of functionalized pyrroles can be prepared in a selective manner from simple and easily accessible precursors. [reaction: see text]

/pdf/copper-catalyzed-vinylation-of-hydrazides-a-regioselective-4x4ue2r6bz.pdf

Marta Rodriguez Rivero

Papers

Domino Cu-Catalyzed CN Coupling/Hydroamidation: A Highly Efficient Synthesis of Nitrogen Heterocycles†

Copper-catalyzed vinylation of hydrazides. A regioselective entry to highly substituted pyrroles.

Copper-Catalyzed Vinylation of Hydrazides. A Regioselective Entry to Highly Substituted Pyrroles.

Domino Cu-Catalyzed C—N Coupling/Hydroamidation: A Highly Efficient Synthesis of Nitrogen Heterocycles.