Reductive monoalkylation of aromatic and aliphatic nitro compounds and the corresponding amines with nitriles.

[reaction: see text] A simple, selective, rapid, and efficient procedure for the synthesis of secondary amines from the reductive alkylation of either aliphatic or aromatic nitro compounds and the corresponding amines is reported. Ammonium formate is used as the hydrogen source and Pd/C as the hydrogen transfer catalyst. The reaction is carried out at room temperature. The rate differences for the preferential formation of secondary over tertiary products are due to both steric and electronic factors.

[1]  H. Sajiki,et al.  Reductive and catalytic monoalkylation of primary amines using nitriles as an alkylating reagent. , 2004, Organic letters.

[2]  W. J. Wheeler,et al.  Synthesis of 14C-labeled 4-hydroxyindole as an intermediate for the preparation of (S)-2-[4-[2-[3-(indol-2-[14C]-4-yloxy)-2-hydroxypropylamino]-2-methylpropyl]-phenoxy]pyridine-5-carboxamide (LY368842-[indole-14C]) glycolate , 2002 .

[3]  K. W. Jung,et al.  Synthesis of Secondary Amines , 2001 .

[4]  Long-hu Zhou,et al.  A novel reductive cyclization of arylmethylidenemalononitrile promoted by samarium diiodide , 1998 .

[5]  Siswanto.,et al.  Selective N-Alkylation of Aniline by Micellar Catalysis , 1997, Journal of colloid and interface science.

[6]  J. Stalewski,et al.  Synthesis of 7,8-Dimethoxy-2-oxo-1,3,4,5-tetrahydropyrrolo[4,3,2-de]quinoline: A Key Intermediate en Route to Makaluvamines, Discorhabdin C and Other Marine Alkaloids of this Group via Vicarious Nucleophilic Substitution of Hydrogen , 1997 .

[7]  S. Narayanan,et al.  Characterization and aniline alkylation activity of vanadia and silica-supported vanadia catalysts , 1995 .

[8]  S. Narayanan,et al.  Vapour phase aniline alkylation activity and selectivity over H-ZSM-5 , 1994 .

[9]  Yoichi M. A. Yamada,et al.  Syntheses of (S)-(−)-pindolol and [3′-13C]-(R)-(−)-pindolol utilizing a lanthanum-lithium-(R)-BINOL ((R)-LLB) catalyzed nitroaldol reaction , 1994 .

[10]  P. Prados,et al.  Synthesis of secondary amines by rhodium catalyzed hydrogenation of nitriles , 1991 .

[11]  Geoffrey A. Lindsay,et al.  Second‐order nonlinear optical measurements in guest‐host and side‐chain polymers , 1990 .

[12]  M. Somei,et al.  The Chemistry of Indoles. XVI. A Convenient Synthesis of Substituted Indoles carrying a Hydroxy Group, a Halogeno Group, or a Carbon Side Chain at the 4-Position via 4-Indolediazonium Salts and a Total Synthesis of (±)-6,7-Secoagroclavine , 1981 .

[13]  D. Nandi,et al.  Pressure Synthesis of N,N-Diethylanlline , 1975 .

[14]  A. B. Brown,et al.  CATALYTIC ALKYLATION OF ANILINE , 1924 .