Amines aryl isocyanides

The Ugi-4CR between (E)-cinnamaldehyde, amines, cyclohexyl isocyanide, and chloroacetic acid afforded N-substituted 2-amino-4-phenylbutenoic amides 55 which were cyclized in basic medium to N-substituted 2-(phenylethenyl)-4-oxoazetidine-2-carboxamides 57 via the highly delocalized intermediate anion 56 [47]. When R was an electron-poor aryl group, the f-lactam ring underwent a rearrangement to give succinimides 58 (Scheme 2.22) [48]. 

Rhenium(III) complexes, 143-164 cyanides, 143 alkyl isocyanides, 143 amides, 144 amidines, 146 amines, 144 arsines, 147 aryl isocyanides, 143 cyanates, 145 diazines, 144 diethyidicarbamato, 150 P-diketones, 149 dinitrogen, 144 N heterocycles, 144 nitriles, 146... 

Pyridine iV-oxides can be aminated with isocyanides (Scheme 33). The reaction proceeds through an N-formylaminopyridine intermediate that can be isolated or hydrolyzed with acid to provide the aminopyridines.The reaction works with a number of substituted pyridines however, with electron-withdrawing groups the yields are lower. With C-3 substituted pyridine iV-oxides, a mixture of regioisomers was produced. The C-2 product predominated with aryl isocyanides. Steric hindrance did appear to impact the yield for both aryl and aliphatic isocyanides. Finally, isoquinoline AT-oxide reacted under these conditions to form the aminoisoquinoline in good yield (60%). If both the two and six positions were blocked, the reaction failed to proceed (14JOC2274). 

The diiodoplatinum(ii) complex with two aryl isocyanide ligands at the /r / .r-positions undergoes nucleophilic addition of a secondary amine to the GN bond to yield a complex having two diaminocarbene ligands (422, Scheme The reaction using a primary amine causes similar addition of amine and subsequent intra-... 

Dehydration of alkyl and aryl iV-formyl compounds with POCI3 is one of the more general routes to alkyl and aryl isocyanides (eq 23). A base, typically an amine base or Potassium t-Butoxide, is also required. The method is simple and effective, although less useful for small, volatile isocyanides than other techniques. The Bischler-Napieralski reaction can occur preferentially to isocyanide formation. ... 

The addition of hydrogen fluoride to an aromatic isocyanide dichloride provides a route to the respective aryl-Af tnfluoromethyl amine [34] (equation 24)... 

The 2,3-substituted indols are formed via a palladium-catalyzed coupling reaction of aryl halide, o-alkenylphenyl isocyanide, and amine (Equation (122)).481 Oxidative addition of an aryl halide, insertion of both the isonitrile and alkene moieties of o-alkenylphenyl isocyanide, and 1,3-hydrogen migration may form a 7r-allylpalladium species, which is then attacked by an amine to afford an indol. 

Di-2-pyridyl sulphite (343) (from 2-pyridone and thionyl chloride in the presence of triethylamine) transforms primary aliphatic and aromatic amines RNH2 into N-sulphinylamines RN=S=0 and it dehydrates amides ArCONH2 to aryl cyanides, aldehyde oximes RCH=NOH (R = Cxlf 7. 4-MeOCgH4 or PhCH=CH) to the cyanides RCN and A-alkyl- and TV-ary Iformamides RNHCHO to isocyanides RNC. Aliphatic and aromatic... 

The nitro group of aromatic nitro compounds has been removed with sodium bor-ohydride. This reaction involves an addition-elimination mechanism. Reduction of the C—N bond on aromatic amines with Li metal in THF generates the aryl compounds.Sodium nitrite, sodium bisulfite in EtOH/water/acetic acid does a similar reduction.Conversion of the aniline derivative to the methanesulfona-mide and subsequent treatment with NaH and NH2CI gives the same result. The BuaSnH reagent also reduces isocyanides, RNC (prepared from RNH2 by for-mylation followed by 17-31), to a reaction that can also be accomplished... 

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