C–CN bond formation: an overview of diverse strategies
TL;DR: A comprehensive review of C-CN bond forming reactions via different approaches is provided in this paper, which 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.
About: This article is published in Chemical Communications.The article was published on 2021-03-02 and is currently open access. It has received 32 citations till now. The article focuses on the topics: Cyanation.
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TL;DR: In this paper, a review summarizes the advances in the development of 1,3-difunctionalization of alkenes mediated by Pd-, Ni-, Fe-, and Cu-based catalysts, with an emphasis on the reaction mechanisms and factors governing regioselectivity.
Abstract: The direct difunctionalization of alkenes has emerged as a sustainable and versatile strategy for the efficient construction of complex molecules from simple chemical feedstocks. Specifically, the 1,3-difunctionalization of alkenes enables the simultaneous installation of functional groups at the non-classical 1,3-position of alkenes. Thus, these chemical transformations create new bond disconnection strategies in chemical synthesis. This emerging strategy has identified a novel pathway for the further development of alkene transformations, and has even been applied to the synthesis of various complex biologically active molecules and pharmaceutical candidates. This review summarizes the advances in the development of 1,3-difunctionalization of alkenes mediated by Pd-, Ni-, Fe-, and Cu-based catalysts, as well as under metal-free conditions, over the past few decades, with an emphasis on the reaction mechanisms and factors governing regioselectivity.
22 citations
TL;DR: In this paper, an In(III)-based metal-organic framework (MOF) 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
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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TL;DR: In this article , a nickel-catalyzed synthesis of an aryl nitrile via an exchange between an aromatic amide and a simple nitric acid was developed.
Abstract: Herein, a nickel-catalyzed synthesis of an aryl nitrile via aryl exchange between an aromatic amide and a simple nitrile was developed. By using cheap, easy-to-handle, and low-toxic 4-cyanopyridine as the cyanating source, cyanation of various aromatic amides afforded an assortment of aryl nitriles including bioactive drugs and organic luminescent molecules in good yields. The reaction exhibited wide substrate scope, good functional group tolerance, and unique selectivity that were complementary to traditional methods. Moreover, two key nickel complexes formed by oxidative addition to each substrate are obtained and determined by X-ray crystallography, which gave strong support for the mechanism elucidations.
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TL;DR: This research presents a novel, scalable, and scalable approaches that can be applied to the rapidly changing and rapidly changing environment of drug discovery and development.
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
1,058 citations
TL;DR: A critical review of the important developments in palladium-catalyzed cyanation of Ar-X from 2000 until 2010 concludes that this methodology is the most popular for preparation of substituted aromatic nitriles.
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).
548 citations
TL;DR: 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, which possess several different structural motifs, and the shorter the bridge, the stronger the interaction.
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.
485 citations
TL;DR: The first cobalt-catalyzed cyanation, halogenation, and allylation via C-H activation have been realized using a bench-stable Co(III) catalyst, resulting in high regio- and mono-selectivity.
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.
457 citations
TL;DR: A copper-catalyzed radical relay pathway for enantioselective conversion of benzylic C–H bonds intobenzylic nitriles is reported, providing evidence for diffusible organic radicals and highlighting the difference between these reactions and C-H oxidations mediated by enzymes and other catalysts that operate via radical rebound pathways.
Abstract: Direct methods for stereoselective functionalization of sp3-hybridized carbon–hydrogen [C(sp3)–H] bonds in complex organic molecules could facilitate much more efficient preparation of therapeutics and agrochemicals. Here, we report a copper-catalyzed radical relay pathway for enantioselective conversion of benzylic C–H bonds into benzylic nitriles. Hydrogen-atom abstraction affords an achiral benzylic radical that undergoes asymmetric C(sp3)–CN bond formation upon reaction with a chiral copper catalyst. The reactions proceed efficiently at room temperature with the benzylic substrate as limiting reagent, exhibit broad substrate scope with high enantioselectivity (typically 90 to 99% enantiomeric excess), and afford products that are key precursors to important bioactive molecules. Mechanistic studies provide evidence for diffusible organic radicals and highlight the difference between these reactions and C–H oxidations mediated by enzymes and other catalysts that operate via radical rebound pathways.
416 citations