20600-55-9

Upstream product

• 536-90-3 m-Anisidine 
• 27153-17-9 3-Methoxy-formanilid 

Downstream Products

• 87681-56-9 Fe(SPh)(m-CNC6H4OMe)2(η-C5H5) 
• 255897-33-7 N-(3-methoxyphenyl)-1,1-diphenylmethanimine 
• 13031-49-7 N-(3-methoxyphenyl)benzamide 

Relevant academic research and scientific papers

Isocyanide 2.0

The isocyanide functionality due to its dichotomy between carbenoid and triple bond characters, with a nucleophilic and electrophilic terminal carbon, exhibits unusual reactivity in organic chemistry exemplified for example in the Ugi reaction. Unfortunately, the over proportional use of only a few isocyanides hampers novel discoveries about the fascinating reactivity of this functional group. The synthesis of a broad range of isocyanides with multiple functional groups is lengthy, inefficient, and exposes the chemist to hazardous fumes. Here we present an innovative isocyanide synthesis overcoming these problems by avoiding the aqueous workup which we exemplify by parallel synthesis from a 0.2 mmol scale performed in 96-well microtiter plates up to a 0.5 mol multigram scale. The advantages of our methodology include an increased synthesis speed, very mild conditions giving access to hitherto unknown or highly reactive classes of isocyanides, rapid access to large numbers of functionalized isocyanides, increased yields, high purity, proven scalability over 5 orders of magnitude, increased safety and less reaction waste resulting in a highly reduced environmental footprint. For example, the hitherto believed to be unstable 2-isocyanopyrimidine, 2-acylphenylisocyanides and even o-isocyanobenzaldehyde could be accessed on a preparative scale and their chemistry was explored. Our new isocyanide synthesis will enable easy access to uncharted isocyanide space and will result in many discoveries about the unusual reactivity of this functional group. This journal is

Visible-light-induced radical cascade cyclization of oxime esters and aryl isonitriles: Synthesis of cyclopenta[: B] quinoxalines

A visible-light-induced radical cascade cyclization of aryl isonitriles and cyclobutanone oxime esters for the synthesis of cyclopenta[b]quinoxalines has been accomplished for the first time. The key to the success of this process was the integration of the in situ-formed nitrile radical followed by the cascade radical isonitrile/nitrile insertion-cyclization. The easy introduction of substituents for both substrates and the high functional group tolerance of the reaction make it an efficient strategy to give various quinoxaline derivatives in moderate to good yields.

Palladium-Catalyzed Diarylation of Isocyanides with Tetraarylleads for the Selective Synthesis of Imines and α-Diimines

Using tetraaryllead compounds (PbAr4) as arylating reagents, isocyanides undergo selective diarylation in the presence of palladium catalysts such as Pd(OAc)2 or Pd(PPh3)4 to afford imines and/or α-diimines based on the isocyanide employed. With aliphatic isocyanides, imines are obtained preferentially, whereas α-diimines are formed in the case of electron-rich aromatic isocyanides. The differences in imine/α-diimine selectivity can be attributed to the stability of imidoylpalladium intermediates formed in this catalytic reaction. Compared with other arylating reagents, tetraaryllead compounds are excellent candidates for use in the selective transformations to imines and/or α-diimines, especially in terms of inhibiting the oligomerization of isocyanides, which results in a lower product selectivity in many transition-metal-catalyzed reactions of isocyanides.

Silver-Catalyzed Chemoselective [4+2] Annulation of Two Isocyanides: A General Route to Pyridone-Fused Carbo- and Heterocycles

A silver-catalyzed chemoselective [4+2] annulation of aryl and heteroaryl isocyanides with α-substituted isocyanoacetamides was developed for the facile and efficient synthesis of 2-aminoquinolones, naphthyridines, and phenanthrolines. A mechanism for this multistep domino reaction is proposed on the basis of a13C-labeling experiment, according to which an unprecedented chemoselective heterodimerization of two different isocyanides generates an α-amidoketenimine intermediate, which undergoes 1,3-amino migration to form an α-imidoylketene, followed by 6 π electrocyclization.

Radical perfluoroalkylation - Easy access to 2-perfluoroalkylindol-3-imines-via electron catalysis

Arylisonitriles (2 equivalents) react with alkyl and perfluoroalkyl radicals to form 2-alkylated indole-3-imines via two sequential additions to the isonitrile moiety followed by homolytic aromatic substitution. The three component reaction comprises three C-C bond formations. The endocyclic imine functionality in the products is more reactive in follow up chemistry and hydrolysis of the exocyclic imine leads to 3-oxindoles that show fluorescence properties.

C-F Activation in Perfluorinated Arenes with Isonitriles under UV-Light Irradiation

Due to the great value of fluorinated arenes in agrochemistry, medicinal chemistry and materials science, development of methods for preparation of fluorinated arenes is of high importance. They can be either accessed by arene fluorination or by partial arene defluorination. However, the carbon-fluorine bond belongs to the strongest σ-bonds, which renders C-F activation highly challenging. Here it is shown that aryl and alkyl isonitriles efficiently activate the strong C-F bond in perfluoroarenes by simple UV irradiation under mild conditions. Reactions proceed by formal direct insertion of the isonitrile into the C-F bond without any transition metal. Activation occurs at arene C-F bonds whereas aliphatic C-F bonds remain unreacted. For selected perfluoroarenes C-F activation occurs with high regioselectivity and resulting imidoyl fluorides are transformed into other valuable compounds. Theoretical studies give insights into the reaction mechanism.