This review is focused on the analysis of current data on new methods of alkenylation of arenes and heteroarenes with alkynes by transition metal catalyzed reactions, Bronsted/Lewis acid promoted transformations, and others. The synthetic potential, scope, limitations, and mechanistic problems of the alkenylation reactions are discussed. The insertion of an alkenyl group into aromatic and heteroaromatic rings by inter- or intramolecular ways provides a synthetic route to derivatives of styrene, stilbene, chalcone, cinnamic acid, various fused carbo- and heterocycles, etc.

Alkenylation of Arenes and Heteroarenes with Alkynes.

Aryl nitriles are found wide applications in natural products, pharmaceuticals, agrochemicals, dyes, and herbicides. Moreover, because the cyano group can be easily converted into various functional groups, aryl nitriles are important intermediates in synthetic organic chemistry. Consequently, the development of new methodologies for the synthesis of aryl nitriles is of significant interests. The traditional methods for their synthesis include Sandmeyer reactions, Rosenmund-von Braun reactions, dehydration reactions of aldoximes and amides. In recent years, numerous efforts have been devoted to the transition-metal-catalyzed cyanation reactions of aryl (pseudo)halides, organometallic reagents and aryl C-H bonds. A number of cyanating reagents have been explored for such transformations, including metal cyanides and organic cyano group sources. In addition, styrene and aryl-substituted alkynes are successfully converted into aryl nitriles through the C-C double or triple bond cleavage. Various benzylic compounds have also been reported for the synthesis of aryl nitriles, such as benzylic halides, alcohols, amines and azides. Furthermore, direct conversion of the methyl group of toluene derivatives into cyano group has also drawn attentions. In this critical review, we summarize the recent developments and useful applications in this field and their mechanisms are also briefly discussed.

Recent Advances in the Synthesis of Aryl Nitrile Compounds

Transition metal-catalyzed direct functionalization of C–H bonds has recently emerged as a powerful strategy for the construction of carbon–carbon and carbon–heteroatom bonds. Among various metals employed, base metal copper has attracted significant attention owing to its relatively low cost, abundance, and versatile reactivity. This review aims to comprehensively summarize the recent advances in copper-mediated (both stoichiometric and catalytic) chelation-assisted functionalization of unactivated C–H bonds.

Recent advances in copper-mediated chelation-assisted functionalization of unactivated C–H bonds

N,N-Dimethylformamide (DMF) is frequently used as an aprotic solvent in chemical transformations in laboratories of academia as well as in those of chemical industry. In the present review, we will reveal that DMF is actually something much more than a solvent. It is a unique chemical since, as well as being an effective polar aprotic solvent, it can play three other important roles in organic chemistry. It can be used as a reagent, a catalyst, and a stabilizer.

/pdf/beyond-a-solvent-triple-roles-of-dimethylformamide-in-21kmffy9kv.pdf

Beyond a solvent: triple roles of dimethylformamide in organic chemistry

Major new advances in synthetic chemistry methods are typically reported using simple, non-standardized reaction substrates, and reaction failures are rarely documented. This makes the evaluation and choice of a synthetic method difficult. We report a standardized complex molecule diagnostic approach using collections of relevant drug-like molecules which we call chemistry informer libraries. With this approach, all chemistry results, successes and failures, can be documented to compare and evolve synthetic methods. To aid in the visualization of chemistry results in drug-like physicochemical space we have used an informatics methodology termed principal component analysis. We have validated this method using palladium- and copper-catalyzed reactions, including Suzuki–Miyaura, cyanation and Buchwald–Hartwig amination.

/pdf/chemistry-informer-libraries-a-chemoinformatics-enabled-15nyyeslda.pdf

Chemistry informer libraries: a chemoinformatics enabled approach to evaluate and advance synthetic methods

Copper-mediated cyanation reactions

Copper-mediated cyanation of aryl boronic acids using benzyl cyanide

A general and efficient synthesis of indeno[1,2]furans via a Pd-catalyzed bicyclization reaction between 2-alkynyliodobenzenes and propargylic alcohols is described. The procedure furnishes indeno[1,2]furans with moderate to excellent yields (51%–78%) and a broad substrate scope. The cascade process combines the formation of one C–O bond and two C–C bonds in a single step.

Synthesis of indeno[1,2-c]furans via a Pd-catalyzed bicyclization of 2-alkynyliodobenzene and propargylic alcohol.

The reaction is proposed to proceed via oxidative insertion of palladium into the aryl—halogen bond followed by complexation to the propargylic alcohol, two subsequent syn-palladations, and a final reductive elimination, generating one C—O and two C—C bonds in a single synthetic step.

Synthesis of Indeno[1,2-c]furans via a Pd-Catalyzed Bicyclization of 2-Alkynyliodobenzene and Propargylic Alcohol.

Aryl nitriles can be efficiently synthesized through transition-metal-mediated cyanation of aryl halides, arenes, aryl boronic acids, and so on. Among those most commonly used transition-metals, copper catalysts are surely much more inexpensive and easier to handle, compared to any other metal catalysts. Considering the high-efficiency of copper catalysts in the activation of C–X, C–H, and C–B bond as well as in the formation of C–CN bond, this Letter summarizes various copper-mediated cyanations based on the different kinds of cyanide reagents, such as metal cyanides, potassium hexacyanoferrate(II), acetone cyanohydrins, DDQ, AIBN, benzyl cyanide, malononitrile, nitromethane, and DMF. Our group’s recent contributions to this area are also demonstrated.

Copper‐Mediated Cyanation Reactions

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