Cyclohexyl isonitrile

Isonitriles are widespread metabolites in marine organisms, although little attention has been paid to their degradation. Pseudomonas putida strain N-19-2 can hydrolyze isonitriles to N-substituted formamides (Goda et al. 2001), and the enzyme is active toward cyclohexyl isonitrile and benzyl isonitrile. 

On treatment of 2,3 4,5-di-0-isopropylidene-D-xylose with cyclohexyl isonitrile and ammonium acetate, 2-acetamido-N-cyclohexyl-2-deoxy-3,4 5,6-di-0-isopropylidene-D-gulonamide was formed112 it was reported that only one isomer was produced in this reaction. 

The intramolecular Ugi reaction of 6-oxo-4-thiacarboxylic acids 212, benzylamine, and cyclohexyl isonitrile gave hexahydro-l,4-thiazepin-5-ones 213, in some cases with high stereoselectivity (Equation 16) <2003JOC3315>. 

The triethylphosphine derivative 14b formed in reaction 12 has a configuration opposite to that of the starting material, as can be seen by comparing the chiroptical properties of 13a and 14b and of the products of Scheme 12 when cyclohexyl isonitrile is used instead of triethylphosphine28,29 ... 

The reaction of trans-PdI(PPh2Me)2Me with cyclohexyl isonitrile occurs readily at RT ... 

Ketenimine complexes can serve as three-atom components in [3 + 2] cycloadditions. The reaction of the tungsten complex (378) with cyclohexyl isonitrile and phenyl isocyanate produces the heterocyclic carbene complex (379), which is the result of the in situ trapping of a ketenimine complex with the isocyanate. Complexes of the type (379) can be oxidatively cleaved to give the previously inaccessible 5-ethoxyhydantoins. [3 + 2] Cycloadditions of this type have also been carried out with aldehydes. 

McFarland, J. W. Reactions of cyclohexyl isonitrile and isobutyraldehyde with various nucleophiles and catalysts. J. Org. Chem. 1963, 28, 2179-2181. 

Cyclopentanecarboxylates. These substances can be prepared by the reaction of 1,3-diiodopropane with an or,/3-unsaturated ester in the presence of copper and an isonitrile (f-butyl isonitrUe or cyclohexyl isonitrile). ... 

Very recently, a polymer-supported construct for quantifying the reactivity of monomers involving multicomponent Ugi strategies was reported [53]. The authors investigated the Ugi four-component condensation of a set of aldehydes, acids, and isonitriles. The amine compound used was bound to a specially modified Rink amide polystyrene resin bearing an ionization leveler and bromine functionality as a mass splitter for accurate analysis by positive electrospray ionization mass spectrometry. The microwave-assisted experiment was performed with a set of ten carboxylic acids, hydrocinnamaldehyde, and cyclohexyl isonitrile in DCM-... 

To a three-necked flask were added 300 mL anhydrous ether and 4.6 g sodium ribbons (0.2 mol), followed by 25.5 mL ethyl acetoacetate (0.2 mol) dropwise under well stirring. Then an additional 300 mL anhydrous ether was added, and the reaction mixture was refluxed for 4 h. Then 25.5 mL freshly distilled cyclohexyl isonitrile (0.2 mol) was added dropwise to the resulting viscous mixture. After being refluxed for 50 h, the reaction mixture... 

Tricyclopentadienyl rare earth cyclohexyl isonitrile complexes have been prepared by addition of cyclohexyl isonitrile to the corresponding tris(cyclopentadienyl) rare earth compounds in benzene. They show definite melting points and are sublimable in vacuum at about 150 to 160°C (E.O. Fischer and H. Fischer, 1965a, 1966 Von Ammon and Kanellakopulos, 1972) ... 

The cyclohexyl isonitrile complexes of the tris(methylcyclopentadienyl) cerium, praseodymium, and neodymium compounds have been mentioned in a discussion of the NMR spectra of these and the corresponding tricyclopentadienyl rare earth complexes, which showed that the AG values of the fluxionality of the cyclohexyl ligands decreased in contrast to those of the unsubstituted cyclopentadienyl derivatives (R.D. Fischer, 1979). 

The methyl nickel complex [NiMecp(PPhj)] reacts with cyclohexyl isonitrile to give the insertion product ... 

FIGURE 7.11 Hydration reaction of cyclohexyl isonitrile catalyzed by the hexameric capsule and inhibited by the presence of tetraethylammomum cation as a competitive guest for the cavity. (Adapted from Ref. [53].)... 

In particular, the reaction between cyclohexyl isonitrile and the TMSNj was investigated both in the presence and in the absence of the hexameric capsule in water-saturated chlorofotm-d. While the reaction did not occur spontaneously, in the presence of a catalytic amount of capsule (10 mol%), the reaction was complete in slightly more than 6 h (Fig. 7.14). Also in this case, rigid control experiments like the use of a weak Brpnsted acid of comparable acidity of the capsule and the use of resorcinol as a H-bond activating species similar to res-orcin[4]arene did not justily the catalytic activity observed. Experiments in the presence of the capsule occupied by a competitive tetraethylammonium guest showed a marked decrease of product formation after the same reaction time (33% yield), confirming the andal role of the encapsulation in the catalytic activity of the supramolecular capsule. 

Multiple, successive insertion of isonitriles into the palladium-carbon o--bond has also been found with organopalladium(II)bis(phosphine) complexes. However, unlike the Ni- catalyzed polymerization, only single, double, and triple insertion reactions of isonitriles have been reported for Pd-mediated reactions. For instance, reaction of methylpalladium(II) complex 2 with cyclohexyl isonitrile in ratios of 1 1, 1 2, and 1 3 afforded selectively single (3), double (4), and triple (5) insertion products, respectively (Scheme 3). However, no further insertion of cyclohexyl isonitrile to 5 took place. No reactivity of the triple insertion complex 5 was explained by the intramolecular coordination of the nitrogen atom of the third imino group, which formed a stable five-mem-bered chelating palladium complex. 

Scheme 44.2 Reactions of/ac-[Re -H2B(tim )2 (CO)3] (5) with ethylenediamine and cyclohexyl isonitrile (tim = 2-mercapto-l-methylimidazolyl) [38, 39]. (See insert for color representation of the figure.)...

---