38644-58-5

Upstream product

• 100-65-2 N-Phenylhydroxylamine 
• 513-81-5 2,3-dimethyl-buta-1,3-diene 
• 98-95-3 nitrobenzene 
• 98-83-9 isopropenylbenzene 
• 625-27-4 2-methyl-2-pentene 

Relevant academic research and scientific papers

Photoassisted, iron-catalyzed allylic amination of olefins with nitroarenes

Olefins react with nitroarenes and carbon monoxide photochemically in the presence of [Cp*Fe(CO)2]2 (Cp=η5-C5Me5) to produce N-aryl-N-allyl amines in moderate to good yields. Unsymmetrical olefins react highly regioselectively with N-functionalization at the less substituted vinylic carbon. Mechanistic probes using 2′-nitrobiphenyl, 2,3-dimethylbutadiene and nitrosobenzene suggest that neither aryl nitrenes nor nitrosoarenes are the active aminating agents in these reactions.

Iron-catalyzed allylic C-H amination of substituted 1,3-dienes

A catalytic method for the selective allylic C-H amination of dienes and trienes using arylhydroxylamines has been developed. This iron-catalyzed approach involves the in situ generation of activated nitrosoarenes, which in turn react with dienes or trienes to give the corresponding aminomethyl dienes or trienes as the major products, and hetero-Diels-Alder adducts as minor products. The selectivity depends on the structures of both the catalyst and the substrate. We have also studied substituent effects using p-substituted phenylhydroxylamines. Copyright

Cu(I)/Cu(II)-catalyzed allylic amination of alkenes

Allylic hydrocarbons are selectively converted to the corresponding allyl amines in good to excellent yield by reaction with aryl hydroxylamines catalyzed by a 1:1 mixture of CuCl and CuCl2 (10 mol %). Under these conditions unsymmetrical olefi

Nitrosoarene-Cu(I) complexes are intermediates in copper-catalyzed allylic amination

Reactions of nitrosobenzene and N,N′-diethyl-4-nitrosoaniline with [Cu(CH3CN)4]PF6 produce novel homoleptic Cu(I)-nitrosoarene complexes, [Cu(ArNO)3]PF6, 1 (Ar = Ph) and 2 (Ar = 4-Et2NC6H4NO). The X-ray structure of 2 reveals that the copper is coordinated in a severely distorted trigonal planar geometry to the N-atom of the nitrosoarene ligand. Reactions of the PhNO complex 1 with olefins and an olefin/diene mixture provide evidence for its role as an intermediate and possibly the active nitrogen transfer agent in the Cu-catalyzed allylic amination of olefins by aryl hydroxylamines. Copyright

Copper-catalyzed amination of alkenes and ketones by phenylhydroxylamine

The catalytic activity of a number of copper complexes and salts toward allylic amination of alkenes using phenylhydroxylamine as the nitrogen fragment donor has been investigated. The best catalyst is CuCl2·2H2O, which produces moderate yields of allylamines with high regioselectivity resulting from double bond transposition. A mechanism similar to that for the molybdenum and the FePc systems is proposed. The first step in the catalytic cycle is the formation of nitrosobenzene from the oxidation of phenylhydroxylamine by Cu(II). The next step is an ene reaction of the alkene with PhNO to produce an allylhydroxylamine, which is then reduced to the allylamine product by Cu(I), thus regenerating Cu(II). The same system can also transfer the nitrogen fragment to the α-carbon of cyclic ketones; this is accompanied by dehydrogenation in some cases to produce α-aminated, α,β-unsaturated ketones.

On the mechanism of allylic amination catalyzed by iron salts

Iron salts catalyze the allylic amination of alkenes by arylhydroxylamines in moderate to good yields and with high regioselectivity resulting from double-bond transposition. The iron-catalyzed reaction of phenylhydroxylamine with representative alkenes i