1195-99-9Relevant academic research and scientific papers
Method for preparing isonitrile compound
-
Paragraph 0068-0073, (2021/01/30)
The invention discloses a method for preparing an isonitrile compound, and belongs to the field of organic synthesis. According to the method, sodium chlorodifluoroacetate or potassium bromodifluoroacetate is used as a difluoromethyl source and is condensed with primary amine under the action of alkali to obtain an isocyanide target product, so that isocyanide is generated in situ on the primary amine. The reaction raw materials, alkali and solvent used in the method are simple and easy to obtain, wide in source and convenient to operate, do not need special storage and use conditions, the method has the advantages of safety, low cost, high yield, simple process, environmental friendliness and the like, and has important application value in the fields of medicine, protein and polypeptidepreparation, pesticides, high polymer materials, dyes and the like.
Metabolic Fate of the Isocyanide Moiety: Are Isocyanides Pharmacophore Groups Neglected by Medicinal Chemists?
Aprile, Silvio,Galli, Ubaldina,Grosa, Giorgio,Tron, Gian Cesare,Purghè, Beatrice
, p. 955 - 966 (2020/05/18)
Despite the isolation of hundreds of bioactive isocyanides from terrestrial fungi and bacteria as well as marine organisms, the isocyanide functionality has so far received little attention from a medicinal chemistry standpoint. The widespread tenet that isocyanides are chemically and metabolically unstable has restricted bioactivity studies to their antifouling properties and technical applications. In order to confirm or refute this idea, the hepatic metabolism of six model isocyanides was investigated. Aromatic and primary isocyanides turned out to be unstable and metabolically labile, but secondary and tertiary isocyanides resisted metabolization, showing, in some cases, cytochrome P450 inhibitory properties. The potential therefore exists for the secondary and tertiary isocyanides to qualify them as pharmacophore groups, in particular as war-heads for metalloenzyme inhibition because of their potent metal-coordinating properties.
Synthesis of isocyanides by reacting primary amines with difluorocarbene
Si, Yi-Xin,Zhu, Peng-Fei,Zhang, Song-Lin
supporting information, p. 9086 - 9090 (2020/11/30)
A general, convenient, and friendly route for preparing a versatile building block of isocyanides from primary amines is developed. Difluorocarbene, generated in situ from decarboxylation of chlorodifluoroacetate, reacts efficiently with primary amines to produce isocyanides. Various primary amines are well tolerated, including aryl, heteroaryl, benzyl, and alkyl amines, as well as amine residues in amino acids and peptides. Late-stage functionalization of biologically active amines is demonstrated, showing its practical capacity in drug design and peptide modification.
Asmic Isocyanide-Nitrile Isomerization-Alkylations
Alwedi, Embarek,Lujan-Montelongo, J. Armando,Cortés-Mejía, Rodrigo,del Campo, Jorge M.,Altundas, Bilal,Fleming, Fraser F.
, p. 4644 - 4648 (2019/07/31)
Anisylsulfanylmethylisocyanide, Asmic, is a versatile building block whose alkylations provide a range of substituted isocyanides. The anisylsulfanyl group plays a critical role in the sequenced deprotonation-alkylation and the subsequent sulfanyl-lithium exchange. Complexation of the anisylsulfanyl group to BuLi in the presence of TMEDA affords a lithiated isocyanide whose alkylations generate trisubstituted isocyanides. In the absence of TMEDA, BuLi triggers cyanide expulsion to afford a transient carbene; reorientation of cyanide with attack at the carbene affords a lithiated nitrile whose alkylations afford quaternary nitriles. The complexation-induced isocyanide-nitrile rearrangement is exceptionally facile, occurring within 5 min at –78 °C. Detailed mechanistic and computational analyses identify the importance of chelation in the bifurcating mechanism: internal chelation favors cyanide extrusion to form a carbene whereas chelating agents favor arylsulfanyl-lithium exchange to generate a lithiated isocyanide. The combined experimental and computational analyses reveal a new mechanism for isocyanide-nitrile isomerization which provides valuable insight for rapidly assembling substituted isocyanides.
Cyanation of alcohols with diethyl cyanophosphonate and 2,6-dimethyl-1,4-benzoquinone by a new type of oxidation-reduction condensation
Masutani, Kouta,Minowa, Tomofumi,Hagiwara, Yoshiaki,Mukaiyama, Teruaki
, p. 1106 - 1117 (2007/10/03)
Cyanation of various alcohols by a new type of oxidation-reduction condensation is described. Primary alkyl diphenylphosphinites, 2,6-dimethyl-1,4-benzoquinone (DMBQ), and diethyl cyanophosphonate gave the corresponding nitriles in high yields. During the above experiment on cyanation of 4-phenylbutan-2-ol, the unexpected formation of a mixture of nitrile and isocyanide was observed. After careful examination of the reaction conditions, selective synthesis of isocyanides from secondary alcohols was successfully accomplished by the use of zinc oxide (ZnO) as an additive. Reaction of tertiary alcohols provided the corresponding isocyanides exclusively in the absence of an additive. Cyanation of optically active alcohols was tried in order to clarify the stereochemistry of this reaction, and the reaction was thus proved to proceed with the inversion of configuration.
Screw Sense Selective Polymerization of Achiral Isocyanides Catalysed by Optically Active Nickel(II) Complexes
Kamer, Paul C. J.,Nolte, Roeland J. M.,Drenth, Wiendelt
, p. 6818 - 6825 (2007/10/02)
Poly(isocyanides), (RN=Cn, can be prepared from isocyanides, , by the catalytic action of nickel(II) compounds.The main chain of these polymers is a rigid helix.This helical conformation results from a restricted rotation around the single bonds that connect the main-chain carbon atoms.Polymerization of achiral isocyanides generally gives a racemic mixture of left- and right-handed helices, whereas polymerization of optically active isocyanides results in helices with an excess of one screw sense.We describe a procedure for obtaining poly(isocyanides) with predominantly one screw sense, starting from an achiral monomer.A catalyst is prepared by adding an optically active amine to a tetrakis(isocyanide)nickel(II) perchlorate complex.Polymerization of various achiral isocyanides with this catalist yields optically active polymers with an enantiomeric excess up to 83percent.
