Ruthenium tetroxide oxidation of N-acylated alkylamines : A new general synthesis of imides.

A Novel One-Pot Synthesis of Unsymmetrical Acyclic Imides

“…As shown, excellent yields were obtained in the reactions of aliphatic nitriles (entries 1-9). In the case of aryl nitriles, the corresponding amides were also produced as side products, therefore the yields decreased in these cases (entries [10][11][12][13][14][15][16]. We decided to conduct the same reaction with other typical Lewis acids such as AlCl 3 , FeCl 3 , ZnCl 2 , NaHSO 4 , etc.…”

“…The best yields were reported for the acid-catalyzed reaction of anhydrides with amides. 6a Other procedures for the synthesis of acyclic imides involve aminocarbonylation of aryl bromides, 8 reaction of azalactone with oxygen and palladium, 9 ruthenium tetroxide oxidation of N-acylated alkyl amines, 10 and reaction of pentafluorophenyl (PFP) esters with deprotonated amides. 11 The more sophisticated methods involve the treatment of amides with reagents such as dimethyl acetals of amides, 12 N,N-bis(trimethylsilyl)formamide, 13 a,a,a-trichloromethyl carbonyl compounds, 14 diketene, 15 or vinyl esters.…”

Oxidations of Amines, Amides, Ethers, Sulfides, Phosphines, Arsines, Stibines and Miscellaneous Substrates

“…Na(IO 4 )/EtOAc the alkyl group adjacent to the amine group was oxidised, while N-acylpropylamines CH 3 CH 2 CH 2 NH(COR) gave the corresponding imides CH 3 CH 2 CONH(COR) (R=Me, Me(CH 2 ) 2 , Me(CH 2 ) 10 , Me 2 CH, Me 3 C, Cl 3 C, Ph, C 6 H 11 ). Oxidations of RCH 2 NHCO(CH 2 ) 2 Me to RCONHCO(CH 2 ) 2 Me were effected for R=Me 2 CH, ClCH 2 , and of PhCH 2 NHCOMe to PhCONHCOMe, but did not work for the electron-withdrawing groups R=EtOOCCH 2 , NC and EtOOC [66]. The system RuO 2 /Na(IO 4 )/aq.…”

An Efficient Transformation of Cyclic Ene-carbamates into .OMEGA.-(N-Formylamino)carboxylic Acids by Ruthenium Tetroxide Oxidation

“…The first example of this type of reaction was described by Desai and co-workers, 5) who reported one case that attempted the cleavage of a CϭC bond in steroidal enamines. Torii and co-workers 6) revealed the procedure for the RuO 4 oxidative cleavage of enolic olefins including two six-membered nitrogen-containing heterocyles that afforded the carbonyl compounds under the conditions using the substrate in a suspension of CCl 4 and H 2 O in the presence of RuO 2 · xH 2 O and NaIO 4 .On the other hand, we have been working on the transformation of cyclic [7][8][9] and acyclic [10][11][12] N-acyl amines into the corresponding lactams and imides including the natural products [13][14][15][16][17] by the RuO 4 oxidation. The double layer oxidation method using a catalytic amount of RuO 2 hydrate, an excess of a NaIO 4 aqueous solution and ethyl acetate system was established for these purposes in our laboratory.…”

“…On the other hand, we have been working on the transformation of cyclic [7][8][9] and acyclic [10][11][12] N-acyl amines into the corresponding lactams and imides including the natural products [13][14][15][16][17] by the RuO 4 oxidation. The double layer oxidation method using a catalytic amount of RuO 2 hydrate, an excess of a NaIO 4 aqueous solution and ethyl acetate system was established for these purposes in our laboratory.…”