140670-05-9

Upstream product

• 64-18-6 formic acid 
• 2403-22-7 N-Benzyl-N-butylamine 
• 72773-04-7 N-formylbenzotriazole 
• 124-38-9 carbon dioxide 
• 591-50-4 iodobenzene 
• 201230-82-2 carbon monoxide 
• 109-73-9 N-butylamine 

Relevant academic research and scientific papers

Palladium-Catalyzed Solvent-Dependent Divergent Synthesis of Benzylformamides

A palladium-catalyzed carbonylative cascade procedure for the synthesis of benzylformamides from aryl halides has been developed. The properties of the solvent chosen play a decisive role on the selectivity of the outcomes. Non-coordinative solvent facilitates the coordination and insertion of CO to the amino-palladium intermediate which then provides the formamides products. While the use of coordinative solvent leads to the formation of amines. A series of functional groups, including ester, ketone, nitro and cyano, were well tolerated under our conditions. The corresponding benzylformamides products were prepared in moderate to good yields without further optimization. (Figure presented.).

Solvent-promoted catalyst-free: N -formylation of amines using carbon dioxide under ambient conditions

An unprecedented catalyst-free formylation of amines using CO2 and hydrosilanes was developed. The solvent plays a vital role in promoting the interaction of amines with hydrosilanes and subsequent CO2 insertion, thus facilitating the simultaneous activation of N-H and Si-H bonds. Based on relevant mechanistic studies, a plausible mechanism involving a silyl carbamate intermediate is proposed.

Preparation of conformationally restricted β2,2- and β2,2,3-amino esters and derivatives containing an all-carbon quaternary center

β-Amino acids are routinely incorporated into peptidic drugs to increase their stability and to incur conformational biases. However, the synthesis of highly substituted β-amino acids still represents a great challenge. A new approach to their preparation is reported involving a Vilsmeier-Haack reaction with nonaromatic carbon nucleophiles. The highly challenging preparation of contiguous tertiary and all-carbon quaternary centers was successfully used to generate several β2,2,3-amino esters, such as derivatives of homoproline, homoalanine, and homopipecolinic esters.

A kinetic EPR study of the dissociation of 1-carbamoyl-1-methylcyclohexa-2,5-dienyl radicals: Release of aminoacyl radicals and their cyclisation

Hydrogen atom abstraction from 1-carbamoyl-1-methylcyclohexa-2,5-dienes generated the corresponding delocalised 1-carbamoyl-1-methylcyclohexa-2,5-dienyl radicals at temperatures below ca. 300 K. At higher temperatures suitably substituted examples dissociated to produce toluene and aminoacyl (carbamoyl) radicals. Both types of intermediate were detected and characterised in solution by EPR spectroscopy. From measurements of the concentrations of the initial and released radicals, rate constants and Arrhenius parameters for dissociation of 1-carbamoyl-1-methylcyclohexa-2,5-dienyl radicals were determined. It was found that dissociation to give a secondary aminoacyl radical [·C(O)N(R)CH2Ph] took place with a rate constant in the range 50 to 90 s-1 at 300 K. The alternative dissociation of the 1-carbamoyl-1-methylcyclohexa-2,5-dienyl radicals to release methyl radicals and an aromatic amide was much slower and did not compete. Analogous dissociations giving primary aminoacyl radicals [·C(O)NHR] were significantly slower. Aminoacyl radicals with allyl, butenyl or similar side chains underwent cyclisation and, in the case of the 1,2,2-trimethylbut-3-enyl derivative, cyclisation was faster than dissociation of the parent cyclohexadienyl radical throughout the accessible temperature range. Semi-empirical AM1 and ab initio DFT computations indicated the decarbonylations of the aminoacyl radicals did not compete with cyclisations.

Photolytic and Chromium(II)-Promoted Addition Reactions of N-Halogenoformamides with Alkenes

Formamidyl radicals (HCONR) do not intramolecularly abstract hydrogen or cyclise onto aromatic rings, but do add intermolecularly to alkenes.The photolytic addition of N-halogenoformamides to alkenes is inhibited by N-alkylation.However, N-alkyl-N-halogenoformamides add to alkenes in the presence of chromium(II) species.The addition of N-halogenoformamides to alkenes occurs regiospecifically with formamidyl bonding to the less substituted terminus of the alkene.The adducts obtained from N-alkylformamidyls exist as mixtures of rotameric isomers whose configurations have been assigned.The reactivity of the formamidyl radical has been discussed in terms of its conformation and electron state.