Reaction Of Isocyanides Research Articles

A Copper-Catalyzed Synthesis of Functionalized Quinazolines from Isocyanides and Aniline Tri- and Dichloroacetonitrile Adducts through Intramolecular C–H Activation

A novel class of substituted quinazolines were prepared in good yields by a one-pot three-component reaction of isocyanides with adducts of anilines and tri- or dichloroacetonitrile, followed by intramolecular C–H activation, catalyzed by copper(I) iodide with l-proline as a ligand in acetonitrile at room temperature.

One-pot three component isocyanide-based reaction: Synthesis of novel tetracyclic fused furo[2′,3′:4,5]pyrimido[2,1-b][1,3]benzothiazole

A rapid, efficient and benign protocol has been developed for the construction of potentially biologically active furo[2′,3′:4,5]pyrimido[2,1-b][1,3]benzothiazole derivatives as major products along with (3E)-3-[(alkylamino)methylene]-2H-pyrimido[2,1-b][1,3]benzothiazole-2,4(3H)-dione derivatives as minor products using a one-pot, multi-component reaction of isocyanides, aromatic aldehydes and 2-hydroxy-4H-pyrimido[2,1-b][1,3]benzothiazol-4-one. The significant features of this protocol are the readily available and low-cost starting materials, short reaction time, mild reaction conditions, high yield of products and avoidance of toxic solvents and catalysts. Structures of compounds 4b and 5a were confirmed from single crystal X-ray studies.

Rhodium‐Catalyzed Oxidative Coupling Reaction of Isocyanides with Alcohols or Amines and Molecular Oxygen as Oxygen Source: Synthesis of Carbamates and Ureas

The first Rh‐catalyzed aerobic oxidative coupling reaction of isocyanides with alcohols or amines has been developed. The reaction takes place under very mild conditions, by using air as the terminal oxidant and oxygen‐atom source. It provides a simple, efficient, and general method for the construction of N‐arylcarbamates and ureas in an atom‐economic manner. Moreover, the new mechanism, involving α‐diazocarbonyl compounds as carbene precursors and a RhI/RhIII catalytic cycle with oxygen, might open up new avenues in rhodium chemistry.

Reactions of Isocyanides with Metal Carbyne Complexes: Isolation and Characterization of Metallacyclopropenimine Intermediates.

η2-Iminoketenyl species have often been postulated as the intermediates in nucleophile-induced carbyne-isocyanide C-C coupling processes. However, such species are elusive. Here we report direct formation of η2-iminoketenyl complexes from reactions of metallapentalyne with isocyanides. Our studies show that steric effects of N-substituents of the isocyanides play an important role in the stability of the three-membered metallacycles of the η2-iminoketenyl complexes. Sterically bulky isocyanides, such as tert-butyl or 1-adamantyl isocyanides, inhibit bending at the isocyanide nitrogen atoms, a requirement for formation of η2-iminoketenyl structures. Reactions of metallapentalyne with excess isocyanide allow the metal-bridged metallaindene derivativesto be isolated as a result of the isocyanide insertion into the M-Cα σ bond of metallapentalyne.

Silver-mediated radical coupling reaction of isocyanides and alcohols/phenols in the presence of water: unprecedented hydration and radical coupling reaction sequence.

The radical coupling of isocyanides and alcohols/phenols promoted by silver in the presence of water is reported for the first time, which led to the formation of diverse carbamates. In contrast to the well-known 1,1-addition to form imidoyl radicals, a novel reaction mechanism, involving sequential hydration of isocyanides and coupling with alkoxyl/phenoxyl radicals, is disclosed by combining experimental and theoretical studies.

A multicomponent bicyclization reaction of isocyanide, allenoate, imine and water to synthesize pyrrolidine-fused rings

A multicomponent bicyclization of isocyanide, allenoate, imine, and water has been disclosed. This protocol involves the formation of five chemical bonds (two C–C, two C–N, and one C–O), thus providing a new pathway to fused rings.

Free-radical initiated cascade methylation or trideuteromethylation of isocyanides with dimethyl sulfoxides

The methylation or trideuteromethylation reaction of isocyanides with dimethyl sulfoxides in a radical way is developed, which offers a low-cost, easy-operation cascade methylation strategy for the synthesis of phenanthridines or isoquinolines.

Copper‐Catalyzed Cascade Cyclization Reactions of Isocyanides with α‐Diazocarbonyls as N‐Terminal Electrophiles: Efficient Synthesis of 2‐Imidazolines and 1,1′‐Biimidazoles

AbstractThe reactions of α‐diazocarbonyls have been extensively studied and widely applied in organic synthesis acting as 1,3‐dipoles, metal carbene precursors and C‐nucleophiles. However, the utility of the electrophilic capability of their terminal nitrogen has been a challenging problem. Herein, a novel copper‐catalyzed cascade cyclization reaction of isocyanides with α‐diazocarbonyls as N‐terminal electrophiles has been developed for the first time. The reaction involves a sequential intermolecular nucleophilic addition/[3+2] cycloaddition/intramolecular cyclization‐ring‐opening/elimination procedure and provides a new and efficient method for the construction of imidazolines and biimidazoles in a single step from readily available starting materials under very mild conditions.magnified image

ChemInform Abstract: Exploiting the Reactivity of Isocyanide: Coupling Reaction Between Isocyanide and Toluene Derivatives Using the Isocyano Group as an N1 Synthon.

AbstractAn oxidative coupling reaction of isocyanides and methylbenzenes using tetrabutylammonium iodide as a catalyst affords the corresponding benzamides.

ChemInform Abstract: Synthesis of Benzoimidazoquinazolines by Cobalt‐Catalyzed Isocyanide Insertion—Cyclization.

An efficient and practical protocol for the synthesis of benzoimidazoquinazoline amines in moderate to good yields by the reaction of isocyanides and benzo[d]imidazol-anilines via a cobalt-catalyzed isocyanide insertion cyclization reaction into the two N–H active bonds is reported.

Visible-Light-Induced Cascade Reaction of Isocyanides and N-Arylacrylamides with Diphenylphosphine Oxide via Radical C-P and C-C Bond Formation.

An effective photoredox-mediated tandem phosphorylation/cyclization reaction of diphenylphosphine oxide with three types of radical acceptors leads to P(O)Ph2-containing phenanthridines, isoquinolines, and indolin-2-ones by formation of both C-P and C-C bonds. [Ir(ppy)2(dtbpy)]PF6 (1 mol %) was used as the catalyst, CsF or Cs2CO3 as the base, and K2S2O8 as the oxidant. A series of functional groups can be tolerated at room temperature. Moderate to good yields were generated.

Isocyanide-Based Multicomponent Bicyclization with Substituted Allenoate and Isatin: Synthesis of Unusual Spirooxindole Containing [5.5]-Fused Heterocycle.

A three-component bicyclization reaction of isocyanide, substituted allenoate, and isatin has been disclosed. This protocol is proposed to proceed through Michael addition, double cyclization, and [1,5]-hydride shift sequence, thus leading to the formation of two new rings and five new chemical bonds, including C-C, C-O, and C-N bonds.

Efficient synthesis of benzothiophenes by [4+1] cycloaddition of 2-mercaptobenzaldehyde derivatives with isocyanides

We developed a [4+1] cycloaddition reaction of isocyanides with 2-mercaptobenzaldehydes and/or their disulfide derivatives, promoted by LiI·2H2O, to afford benzothiophene derivatives in moderate to good yields. Isocyanides, 2-mercaptobenzaldehydes and disulfide derivatives of various types were used successfully in the reaction.

Multicomponent Synthesis of Novel Class of Isatin and 5-isatinyli-denerhodanine Based Diaminofuran Derivatives

A simple and efficient method has been developed for the synthesis of a new collection of isatin and 5-isatinylidenerhodanine derivatives carrying furan group, from N-(carboxymethyl)isatin through a multi-component reaction is explained. The reactive 1:1 intermediate formed from the reaction of isocyanides and dialkyl acetylenedicarboxylates was trapped at reflux temperature using N-(carboxymethyl)isatin derivatives to produce poly functionalized furan rings in good yields. Keywords: 2, 5-diaminofurans, N-(carboxymethyl)isatin, isocynides, dialkyl acetylenedicarboxylates, rhodanine..

Fe3O4@SiO2-OSO3H nanocomposite as an efficient catalyst for the preparation of tricarboxamides

In this research a highly efficient one-pot preparation of tricarboxamide derivatives via five-component reactions of isocyanides, aldehydes Meldrum’s acid and 2equiv. of amines have been developed in the presence of Fe3O4@SiO2-OSO3H nanocomposite. NanoFe3O4 encapsulated-silica particles bearing sulfonic acid was readily recovered using an external magnet and could be reused several times without significant loss of reactivity. The catalyst was fully characterized by VSM, FT-IR, SEM, XRD, EDX and TEM analysis.

Exploiting the Reactivity of Isocyanide: Coupling Reaction between Isocyanide and Toluene Derivatives Using the Isocyano Group as an N1 Synthon

An unusual oxidative coupling reaction of isocyanide and toluene derivatives using tetrabutylammonium iodide (TBAI) as a catalyst is disclosed. The experimental results and mechanistic study show that the isocyano group acts formally as an N1 synthon during the transformation, thus expanding the reactivity profile of isocyanide.

ChemInform Abstract: Isocyanide Based [4 + 1] Cycloaddition Reactions: An Indispensable Tool in Multi‐Component Reactions (MCRs)

AbstractReview: [73 refs.

ChemInform Abstract: Palladium‐Catalyzed Cross‐Coupling Reaction of Azides with Isocyanides.

AbstractThe cross‐coupling reaction of isocyanides (II) with aryl, heteroaryl, benzyl, and alkyl azides leads to a variety of unsymmetrical carbodiimides in moderate to high yields.

ChemInform Abstract: Silver‐Catalyzed [3 + 2] Cycloaddition of Isocyanides with Diazo Compounds: New Regioselective Access to 1,4‐Disubstituted‐1,2,3‐triazoles.

An unprecedented silver-catalyzed 1,3-dipolar cycloaddition reaction of isocyanides with diazo compounds to afford 1,4-disubstituted 1,2,3-triazoles is reported. This reaction exhibits remarkable features, such as high regioselectivity, mild reaction conditions, easily available substrates with simple operation, and good yields with a broad spectrum of substrates. It constitutes an alternative to the well-known CuAAC click reaction.

Synthesis of benzoimidazoquinazolines by cobalt-catalyzed isocyanide insertion–cyclization

The synthesis of benzoimidazoquinazoline amines by the reaction of isocyanides and benzo[d]imidazol-anilines via a cobalt-catalyzed isocyanide insertion reaction into the two N–H active bonds is reported.