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Open accessJournal ArticleDOI: 10.1039/D0CC07783F

C–CN bond formation: an overview of diverse strategies

02 Mar 2021-Chemical Communications (The Royal Society of Chemistry)-Vol. 57, Iss: 18, pp 2210-2232
Abstract: Nitrile or cyano compounds are an important part of structural motifs in dyes, agrochemicals, medicinal compounds, and electronic materials. Also, aryl nitrile is an important intermediate in the preparation of numerous compounds via transformations such as hydrolysis, hydration, reduction, cycloadditions, and nucleophilic additions. Such methods are beneficial for introducing sensitive functional groups in various positions in the multi-step synthesis of natural products and medicinal compounds. In the past decades, various cyanation methods have been reported in the vast arena of chemistry, which have made several building blocks accessible. Previously reported cyanation reviews, letters, and perspectives are written in parts. Thus, today a comprehensive review that will be able to guide readers through the vast pool of C–CN bond forming reactions via different approaches is obligatory. The present feature article depicts the various areas of cyanation methodologies that are based on the metal catalyst used, directed, non-directed, electrochemical, photochemical, asymmetric, and radical based approaches. This feature article will serve as a comprehensive tool to navigate the C–CN (cyanation) reactions across the vast area in synthetic chemistry.

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Topics: Cyanation (60%)
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6 results found


Open accessJournal ArticleDOI: 10.1002/HLCA.202100200
Abstract: A synthetic method for the palladium-catalyzed cyanation of aryl boronic acids using bench stable and non-toxic Ncyanosuccinimide has been developed. High-throughput experimentation facilitated the screen of 90 different ligands and the resultant statistical data analysis identified that ligand σ–donation, π–acidity and sterics are key drivers that govern yield. Categorization into three ligand groups – monophosphines, bisphosphines and miscellaneous – was performed before the analysis. For the monophosphines, the yield of the reaction increases for strong σ–donating, weak π–accepting ligands, with flexible pendant substituents. For the bisphosphines, the yield predominantly correlates with ligand lability. The applicability of the designed reaction to a wider substrate scope was investigated, showing good functional group tolerance in particular with boronic acids bearing electron-withdrawing substituents. This work outlines the development of a novel reaction, coupled with a fast and efficient workflow to gain understanding of the optimal ligand properties for the design of improved palladium cross-coupling catalysts.

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Topics: Cyanation (65%)

3 Citations


Journal ArticleDOI: 10.1021/ACSAMI.1C09074
Abstract: An In(III) based metal-organic framework (MOF), In-pbpta, with soc topology was constructed from the trigonal prismatic [In3(μ3-O)(H2O)3(O2C-)6] secondary building unit (SBU) and a custom-designed tetratopic linker H4pbpta (pbpta = 4,4',4″,4‴-(1,4-phenylenbis(pyridine-4,2,6-triyl))-tetrabenzoic acid)). The obtained MOF shows a Brunauer-Emmett-Teller surface area of 1341 m2/g with a pore volume of 0.64 cm3/g, which is the highest among the scarcely reported In-soc-MOFs. The constructed MOF demonstrates excellent performance as a heterogeneous Lewis acid catalyst for highly efficient conversion in a one-pot multicomponent Strecker reaction for the preparation of α-aminonitriles under solvent-free conditions, which can be easy to separate and recycle without significant loss of activity for up to seven cycles. The computational modeling studies suggest the presence of the three substrates in close vicinity to the In-oxo cluster. The strong interactions of the aldehyde/ketone and the amine with the In-oxo cluster together with the readily available cyanide ion around the In-oxo cluster lead to high catalytic conversion within a short period of time for the MOF catalyst. Our work therefore lays a foundation to develop MOF as a new class of efficient heterogeneous catalyst for one-pot Strecker reaction.

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2 Citations


Journal ArticleDOI: 10.1039/D1CY00241D
Abstract: Aryl nitriles are key structural motifs in numerous important dyes, agrochemicals, natural products and drug molecules. They are also well known as versatile intermediates for the rapid synthesis of diverse organic compounds such as amines, amidines, tetrazoles, aldehydes, amides and carboxylic acids. In recent years, transition metal-catalyzed sp2 C–H bond cyanation has attracted considerable attention and significant progress has been made in this field. As a major advancement in this field, the directing group strategy in transition metal-catalyzed sp2 C–H bond cyanation has contributed significantly to the direct conversion of cheap hydrocarbons to synthetically versatile cyano-containing compounds, which features the advantages of high efficiency, no pre-functionalization of the substrate, low pollution etc. In this minireview with sections classified by the type of different metal-mediated catalytic systems, we mainly focus on catalytic methodologies of transition metal-catalyzed sp2 C–H bond cyanation assisted by a directing group, with emphasis on reaction scopes, limitations and mechanisms. In addition, the future development prospects of this specific field are also introduced.

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Topics: Cyanation (60%)

1 Citations


Journal ArticleDOI: 10.1002/CHEM.202103384
Abstract: Nitriles are recurring motifs in bioactive molecules and versatile functional groups in synthetic chemistry. Despite recent progress, direct introduction of a nitrile moiety in heteroarenes remains challenging. Recent developments in electrochemical reactions pave the way to more practical cyanation protocols. However, currently available methods typically require hazardous cyanide sources, expensive mediators, and often suffer from narrow substrate scope and laborious reaction set-up. To address the limitations of current synthetic methods, we report here an effective, sustainable, and scalable procedure for the direct C(sp2)-H cyanation of aromatic N-heterocycles with a user-friendly flow-electrochemical set-up. Furthermore, high substrate and functional group tolerance is demonstrated, allowing for late-stage functionalization of drug-like scaffolds such as natural products and pharmaceuticals.

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Topics: Cyanation (59%)

Journal ArticleDOI: 10.1039/D1QO01060C
Qing Yang1, Qing Yang2, Xiao-Tong Yan1, Cheng-Tao Feng1  +4 moreInstitutions (3)
Abstract: An I2O5 promoted tandem Strecker/C(sp3)–H amination reaction of pyridine-2-carboxaldehydes, benzylamines and NH4SCN has been reported. This multicomponent reaction that allows the single-step construction of biologically important cyano-functionalized imidazo[1,5-a]pyridines with molecular diversity was realized for the first time. Moreover, the use of safe and easy-to-handle NH4SCN as a surrogate cyanating agent makes this protocol appealing for potential applications.

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Topics: Amination (62%)

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78 results found


Open accessJournal ArticleDOI: 10.1021/JM100762R
Abstract: Fraser F. Fleming,* Lihua Yao, P. C. Ravikumar, Lee Funk, and Brian C. Shook Department of Chemistry and Biochemistry, Duquesne University, Pittsburgh, Pennsylvania 15282-1530, Mylan Pharmaceuticals Inc., 781 Chestnut Ridge Road, Morgantown, West Virginia 26505, and Johnson & Johnson Pharmaceutical Research and Development, L.L.C., Welsh and McKean Roads, P.O. Box 776, Spring House, Pennsylvania 19477

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920 Citations


Journal ArticleDOI: 10.1039/C1CS15004A
Abstract: The palladium-catalyzed cyanation of Ar–X (X = I, Br, Cl, OTf, and H) allows for an efficient access towards benzonitriles. After its discovery in 1973 and following significant improvements in recent decades, this methodology has become nowadays the most popular for preparation of substituted aromatic nitriles. In this critical review, we summarize the important developments in this area from 2000 until 2010 (151 references).

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Topics: Cyanation (68%)

468 Citations


Journal ArticleDOI: 10.1021/AR0000354
Joel S. Miller1, Jamie L. Manson1Institutions (1)
Abstract: Magnets synthesized from molecules have contributed to the renaissance in the study of magnetic materials. Three-dimensional network solids exhibiting magnetic ordering have been made from several first-row metal ions and bridging unsaturated cyanide, tricyanomethanide, and/or dicyanamide ligands. These materials possess several different structural motifs, and the shorter the bridge, the stronger the interaction (i.e., C⋮N > N⋮CN ≫ N⋮CNC⋮N = N⋮CCC⋮N). Cyanide additionally has the ability to discriminate between C- and N-bonding to form ordered heterobimetallic magnets, and the strong coupling can lead to ferro- or ferrimagnetic ordering substantially above room temperature. Tricoordination of tricyanomethanide results in spin-frustrated systems, which possess interpenetrating rutile-like networks. In contrast, single rutile-like frameworks are formed by μ3-bonded dicyanamide, which leads to ferromagnetics and weak ferromagnetics.

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Topics: Dicyanamide (57.99%), Ferromagnetism (53%)

443 Citations


Journal ArticleDOI: 10.1021/JA511011M
Abstract: The first cobalt-catalyzed cyanation, halogenation, and allylation via C–H activation have been realized. These formal SN-type reactions generate valuable (hetero)aryl/alkenyl nitriles, iodides, and bromides as well as allylated indoles using a bench-stable Co(III) catalyst. High regio- and mono-selectivity were achieved for these reactions. Additionally, allylation proceeded efficiently with a turnover number of 2200 at room temperature, which is unprecedented for this Co(III) catalyst. Alkenyl substrates and amides have been successfully utilized in Cp*Co(III)-catalyzed C–H activation for the first time.

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Topics: Cyanation (65%), Halogenation (59%), Catalysis (51%) ... show more

411 Citations


Journal ArticleDOI: 10.1021/JA0390303
Abstract: RuCl3-catalyzed oxidative cyanation of tertiary amines with sodium cyanide under molecular oxygen (1 atm) at 60 °C gives the corresponding α-aminonitriles, which are versatile synthetic intermediates of various compounds such as amino acids and unsymmetrical 1,2-diamines, in excellent yields. This reaction is clean and should be an environmentally benign and useful process.

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Topics: Cyanation (72%), Sodium cyanide (57.99%)

384 Citations


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