Aryl Isonitriles Research Articles

Palladium-promoted cascade reactions of isonitriles and 6-iodo-N-propargylpyridones: synthesis of mappicines, camptothecins, and homocamptothecins.

Ambient-temperature reactions of electron-rich aryl isonitriles with substituted 6-iodo-N-propargylpyridones in the presence of silver carbonate and palladium acetate produce 11H-indolizino[1,2-b]quinolin-9-ones in good to excellent yield. Experimental evidence suggests that the process occurs though organopalladium rather than radical intermediates. It is applied to synthesis analogues of mappicine and camptothecin, including the silatecans DB-67 and DB-91 (homo-DB-67).

Synthesis of (Boryl)(silyl)iminomethanes by Insertion of Isonitriles into Silicon−Boron Bonds

The insertion of alkyl and aryl isonitriles into the silicon−boron bond of silylboranes proceeded thermally to provide (boryl)(silyl)iminomethanes in moderate-to-good yields. The (boryl)(silyl)iminomethane reacted with borane (BH3) to give the corresponding borane complex in good yield, whose crystal structure was determined by a single-crystal X-ray analysis.

Vinyl isonitriles in radical cascade reactions: formation of cyclopenta-fused pyridines and pyrazines

The 4 + 1 radical annulation reaction of vinyl isonitriles with iodoalkynes or iodonitriles affording cyclopenta-fused pyridines and pyrazines respectively and the first example of an intramolecular radical addition to an aryl isonitrile are described.

An isonitrile-alkyne cascade to di-substituted indoles

Intramolecular tin and sulfur mediated free-radical cyclizations between an aryl isonitrile and a pendant TMS-substituted alkyne give 2,3-disubstituted indoles from 5- exo-dig cyclization and nucleophilic trapping of the resulting indolenine intermediate.

ChemInform Abstract: A General Synthetic Approach to the (20S)‐Camptothecin Family of Antitumor Agents by a Regiocontrolled Cascade Radical Cyclization of Aryl Isonitriles.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

A General Synthetic Approach to the (20S)-Camptothecin Family of Antitumor Agents by a Regiocontrolled Cascade Radical Cyclization of Aryl Isonitriles

The power of radical reactions continues to increase! A cascade radical annulation route now allows perhaps the mildest and most general method for the synthesis of both known and new members of the camptothecin family (parent structure on the right) of antitumor agents.

Aryl isonitrile binding to [Fe4S4] clusters: formation of [Fe4S4]+ and [{Fe4S4}2]2 cores

M. Harmjanz, W. Saak, D. Haase and S. Pohl, Chem. Commun., 1997, 951 DOI: 10.1039/A700613F

Tandem radical reactions of isonitriles with 2-pyridonyl and other aryl radicals: Scope and limitations, and a first generation synthesis of (±)-camptothecin

Photolysis of N-propargyl-6-halo-2-pyridones and related aromatic halides in the presence of aryl isonitriles provides tetra- and penta-cyclic products in a single step by a sequence of radical addition to the isonitrile followed by two cyclizations. The scope and limitations of the process are described along with a first generation synthesis of racemic camptothecin.

Inclusion of Organic Vapors by Crystalline, Solvatochromic [Pt(aryl isonitrile)4][Pd(CN)4] Compounds. "Vapochromic" Environmental Sensors

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTInclusion of Organic Vapors by Crystalline, Solvatochromic [Pt(aryl isonitrile)4][Pd(CN)4] Compounds. "Vapochromic" Environmental SensorsChristopher L. Exstrom, John R. Jr. Sowa, Charles A. Daws, Daron Janzen, Kent R. Mann, Glenn A. Moore, and Frederick F. StewartCite this: Chem. Mater. 1995, 7, 1, 15–17Publication Date (Print):January 1, 1995Publication History Published online1 May 2002Published inissue 1 January 1995https://doi.org/10.1021/cm00049a005RIGHTS & PERMISSIONSArticle Views653Altmetric-Citations162LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (1 MB) Get e-AlertsSupporting Info (3)»Supporting Information Supporting Information Get e-Alerts

Iron(II) complexes with the chelating bidentate isonitrile ligand DiNC

A series of Fe(II) complexes containing the chelating bidentate isonitrile ligand DiNC have been prepared and characterized. Both cis and trans isomers of FeCl 2(DiNC) 2 are obtained from the reaction of FeCl 2·4H 2O with DiNC. One Cl − in cis-FeCl 2(DiNC) 2 is readily substituted by various ligands L to yield the FeCl(L)(DiNC) + 2 complexes, where L = Co, PPh 3, AsPh 3, P(OPh) 3, or C 5H 5N. Mercuric chloride reacts with cis-FeCl 2(DiNC) 2 to give the adduct cis-Fe(DiNC) 2Cl 2·HgCl 2, which is converted to the [FeCl(L)(DiNC) 2] HgCl 3, L = CO or CDMe, salts upon reaction with CO and CNMe. Combination of cis-FeCl 2(DiNC) 2 with the proper stoichiometry of SnCl 2·2H 2O yields the −SnCl 3 complexes, cis-FeCl(DiNC) 2(SnCl 3) and cis-Fe(DiNC) 2(SnCl 3) 2. A comparison of these results with previously known chemistry of related Fe(II) monodentate arylisonitrile complexes indicates that, except for the required cis isonitrile donor geometry of DiNC, the ligand properties of DiNC are very similar to those of related monodentate aryl isonitrile ligands.

An investigation of the reaction between [{Fe(η5–C5H5)(CO)2}2] and aryl isonitriles

The direct reaction between [{Fe(η5-C5H4X)(CO)2}2](X = H, Me, or COOMe) and aryl isonitriles RNC (R = 2,6-Me2C6H3 or C6H5) in refluxing toluene readily yields the tetrasubstituted derivatives [{Fe(η5-C5H4X)(RNC)2}2]. The intermediate derivatives [Fe2(η5-C5H5)2(CO)4–n(RNC)n](n= 1 or 2) can be prepared by the exchange reaction between [{Fe(η5-C5H5)(RNC)2}2] and [{Fe(η5-C5H5)(CO)2}2]. Reaction rates for the substitution of [{Fe(η5= C5H5X)(CO)2}2] by RNC are dependent on both the nature of R and X, and increase with both the nucleophilicity of R and the electron-withdrawing power of X. An alternative route to [Fe2(η5-C5H5)2(CO)4–n(RNC)n](n= 1 or 2) is via the reaction between Na[Fe(η5-C5H5)(CO)2] and 2,6-Me2C6H3NC in the presence of C7H7+BF4–. The isonitrile complexes have been characterized by i.r. and n.m.r. spectroscopy.